U.S. patent number 5,770,664 [Application Number 08/855,510] was granted by the patent office on 1998-06-23 for catalyst component for producing polyolefin, catalyst for producing polyolefin comprising the catalyst component, and process for producing polyolefin in the presence of the catalyst.
This patent grant is currently assigned to Japan Polyolefins Co., Ltd.. Invention is credited to Akihiro Hori, Shintaro Inazawa, Kiyotaka Ishida, Nobuyuki Kibino, Tetsuya Maki, Shigenobu Miyake, Yoshikuni Okumura.
United States Patent |
5,770,664 |
Okumura , et al. |
June 23, 1998 |
Catalyst component for producing polyolefin, catalyst for producing
polyolefin comprising the catalyst component, and process for
producing polyolefin in the presence of the catalyst
Abstract
A catalyst component for producing polyolefin, a catalyst for
producing polyolefin using the catalyst component, and a process
for producing polyolefin in the presence of the catalyst. The
catalyst component comprises a metallocene compound represented by
formula (1): ##STR1## All the symbols in formula (1) are defined in
the description.
Inventors: |
Okumura; Yoshikuni (Oita,
JP), Kibino; Nobuyuki (Oita, JP), Maki;
Tetsuya (Oita, JP), Hori; Akihiro (Oita,
JP), Ishida; Kiyotaka (Oita, JP), Miyake;
Shigenobu (Oita, JP), Inazawa; Shintaro (Oita,
JP) |
Assignee: |
Japan Polyolefins Co., Ltd.
(Tokyo, JP)
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Family
ID: |
17173680 |
Appl.
No.: |
08/855,510 |
Filed: |
May 13, 1997 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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542706 |
Oct 13, 1995 |
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Foreign Application Priority Data
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Oct 13, 1994 [JP] |
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6-248130 |
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Current U.S.
Class: |
526/127; 526/160;
526/150; 526/352; 526/348.2; 526/351; 526/153; 526/133;
526/943 |
Current CPC
Class: |
C08F
10/00 (20130101); C08F 10/02 (20130101); C08F
210/16 (20130101); C08F 10/00 (20130101); C08F
4/65927 (20130101); C08F 10/02 (20130101); C08F
4/65927 (20130101); C08F 4/65904 (20130101); Y10S
526/943 (20130101); C08F 4/65912 (20130101); C08F
4/65916 (20130101); C08F 4/65927 (20130101); C08F
110/02 (20130101); C08F 110/06 (20130101); C08F
4/65908 (20130101); C08F 110/02 (20130101); C08F
2500/11 (20130101); C08F 2500/01 (20130101); C08F
2500/12 (20130101); C08F 210/16 (20130101); C08F
210/14 (20130101); C08F 2500/11 (20130101); C08F
2500/01 (20130101); C08F 2500/12 (20130101); C08F
110/02 (20130101); C08F 2500/12 (20130101); C08F
2500/07 (20130101); C08F 2500/03 (20130101); C08F
2500/11 (20130101); C08F 110/06 (20130101); C08F
2500/03 (20130101); C08F 2500/20 (20130101); C08F
210/16 (20130101); C08F 210/14 (20130101); C08F
2500/08 (20130101) |
Current International
Class: |
C08F
10/00 (20060101); C08F 10/02 (20060101); C08F
110/00 (20060101); C08F 4/00 (20060101); C08F
4/659 (20060101); C08F 110/02 (20060101); C08F
210/00 (20060101); C08F 110/06 (20060101); C08F
210/16 (20060101); C08F 004/64 () |
Field of
Search: |
;526/943,127,160,133,150,153 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0524624A2 |
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Jan 1993 |
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EP |
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0528287A1 |
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Feb 1993 |
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EP |
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0576970A1 |
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Jan 1994 |
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EP |
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Primary Examiner: Nagumo; Mark
Attorney, Agent or Firm: Sughrue, Mion, Zinn, Macpeak &
Seas, PLLC
Parent Case Text
This is a Continuation of application Ser. No. 08/542,706 filed
Oct. 13, 1995 now abandoned.
Claims
What is claimed is:
1. A process for producing a polyolefin, said process comprising
the step of homopolymerizing ethylene or copolymerizing ethylene
and at least one of propylene, 1-butene, 1-hexene or 1-octene, in
the presence of a catalyst comprising:
(A) a catalyst component;
(B) a Lewis acid compound; and
(C) an organoaluminum compound,
said catalyst component comprising a metallocene compound
represented by formula (1): ##STR18## wherein M.sup.1 represents a
transition metal atom selected from the group consisting of Ti, Zr,
and Hf;
X.sup.1 and X.sup.2 are the same or different and each represents a
hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to
20 carbon atoms which may contain a halogen atom, an OR group, an
SR group, an OCOR group, an SO.sub.2 R group, an OSO.sub.2 R group,
or an NRR' group, in which R and R' are the same or different and
each represents a hydrogen atom or a hydrocarbon group having from
1 to 7 carbon atoms which may optionally contain a halogen
atom;
R.sup.1 and R.sup.2 are the same or different and each represents a
hydrogen atom, a hydrocarbon group having from 1 to 20 carbon
atoms, an OR group, or an SR group, in which R represents a
hydrogen atom or a hydrocarbon group having from 1 to 7 carbon
atoms which may optionally contain a halogen atom, R.sup.1 and
R.sup.2 may be connected to each other to form a ring;
R.sup.3 represents a hydrocarbon group having from 1 to 5 carbon
atoms which may contain a silicon atom;
R.sup.4 represents an aryl group having from 6 to 20 carbon atoms
which may contain a silicon atom;
R.sup.5 to R.sup.15 each represents a hydrogen atom;
Y.sup.1 represents a carbon atom, a silicon atom, or a germanium
atom; and
n represents an integer of from 1 to 3.
2. A process for producing a polyolefin as claimed in claim 1,
wherein said catalyst further comprises (D) a particulate
carrier.
3. A process for producing a polyolefin as claimed in claim 1,
wherein R.sub.4 is a phenyl group, a tolyl group, a 2,6-dimethyl
phenyl group, a 2,4,6-trimethyl phenyl group, a naphthyl group or
an anthracenyl group.
4. A process for producing a polyolefin as claimed in claim 3,
wherein R.sub.4 is a phenyl group or a 1-naphthyl group.
5. A process for producing a polyolefin, said process comprising
the step of polymerizing one of propylene, 1-butene, 1-hexene or
1-octene or copolymerizing two or more of propylene, 1-butene,
1-hexene and 1-octene, in the presence of a catalyst
comprising:
(A) a catalyst component;
(B) a Lewis acid compound; and
(C) an organoaluminum compound;
said catalyst component (A) comprising a metallocene compound
represented by formula (1): ##STR19## wherein M.sup.1 represents a
transition metal atom selected from the group consisting of Ti, Zr,
and Hf;
X.sup.1 and X.sup.2 are the same or different and each represents a
hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to
20 carbon atoms which may optionally contain a halogen atom, an OR
group, an SR group, an OCOR group, an SO.sub.2 R group, an
OSO.sub.2 R group, or an NRR' group, in which R and R' are the same
or different and each represents a hydrogen atom or a hydrocarbon
group having from 1 to 7 carbon atoms which may optionally contain
a halogen atom;
R.sup.1 and R.sup.2 are the same or different and each represents a
hydrogen atom, a hydrocarbon group having from 1 to 20 carbon
atoms, an OR group, or an SR group, in which R represents a
hydrogen atom or a hydrocarbon group having from 1 to 7 carbon
atoms which may contain a halogen atom, R.sup.1 and R.sup.2 may be
connected to each other to form a ring;
R.sup.3 represents a hydrocarbon group having from 1 to 5 carbon
atoms which may optionally contain a silicon atom;
R.sup.4 represents an aryl group having from 6 to 20 carbon
atoms;
R.sup.5 to R.sup.15 are the same or different and each represents a
hydrogen atom or a hydrocarbon group having from 1 to 20 carbon
atoms which may optionally contain a silicon atom and optionally
two of R.sup.5 to R.sup.15 are connected to each other to form a
ring;
Y.sup.1 represents a carbon atom, a silicon atom, or a germanium
atom; and
n represents an integer of from 1 to 3.
6. A process for producing a polyolefin as claimed in claim 5,
wherein said catalyst further comprises (D) a particulate
carrier.
7. A process for producing a polyolefin as claimed in claim 5,
wherein R.sub.4 is a phenyl group, a tolyl group, a 2,6-dimethyl
phenyl group, a 2,4,6-trimethyl phenyl group, a naphthyl group or
an anthracenyl group.
8. A process for producing a polyolefin as claimed in claim 7,
wherein R.sub.4 is a phenyl group or a 1-naphthyl group.
9. A process for producing a polyolefin as claimed in claim 5,
wherein said process comprises polymerizing propylene.
10. A process for producing a polyolefin, said process comprising
the step of polymerizing one of propylene, 1-butene, 1-hexene or
1-octene or copolymerizing two or more of propylene, 1-butene,
1-hexene and 1-octene, in the presence of a catalyst
comprising:
(A-1) a catalyst component;
(A-2) an auxiliary metallocene compound;
(B) a Lewis acid compound; and
(C) an organoaluminum compound;
said catalyst component (A-1) comprising a metallocene compound
represented by formula (1): ##STR20## wherein M.sup.1 represents a
transition metal atom selected from the group consisting of Ti, Zr,
and Hf;
X.sup.1 and X.sup.2 are the same or different and each represents a
hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to
20 carbon atoms which may optionally contain a halogen atom, an OR
group, an SR group, an OCOR group, an SO.sub.2 R group, an
OSO.sub.2 R group, or an NRR' group, in which R and R' are the same
or different and each represents a hydrogen atom or a hydrocarbon
group having from 1 to 7 carbon atoms which may optionally contain
a halogen atom;
R.sup.1 and R.sup.2 are the same or different and each represents a
hydrogen atom, a hydrocarbon group having from 1 to 20 carbon
atoms, an OR group, or an SR group, in which R represents a
hydrogen atom or a hydrocarbon group having from 1 to 7 carbon
atoms which may optionally contain a halogen atom, R.sup.1 and
R.sup.2 may be connected to each other to form a ring;
R.sup.3 represents a hydrocarbon group having from 1 to 5 carbon
atoms which may optionally contain a silicon atom;
R.sup.4 represents an aryl group having from 6 to 20 carbon
atoms;
R.sup.5 to R.sup.15 are the same or different and each represents a
hydrogen atom or a hydrocarbon group having from 1 to 20 carbon
atoms which may optionally contain a silicon atom and optionally
two of R.sup.5 to R.sup.15 are connected to each other to form a
ring;
Y.sup.1 represents a carbon atom, a silicon atom, or a germanium
atom; and
n represents an integer of from 1 to 3, and
said auxiliary metallocene compound (A-2) being represented by
formula (3) or (4): ##STR21## wherein M.sup.2 represents a
transition metal atom selected from the group consisting of Ti, Zr,
and Hf;
X.sup.3 and X.sup.4 are the same or different and each represents a
hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to
20 carbon atoms which may optionally contain a halogen atom, an OR
group, an SR group, an OCOR group, an SO.sub.2 R group, an
OSO.sub.2 R group, or an NRR' group, in which R and R' are the same
or different and each represents a hydrogen atom or a hydrocarbon
group having from 1 to 7 carbon atoms which may contain a halogen
atom;
R.sup.18 and R.sup.19 are the same or different and each represents
a hydrogen atom, a hydrocarbon group having from 1 to 20 carbon
atoms, an OR group, or an SR group, in which R represents a
hydrogen atom or a hydrocarbon group having from 1 to 7 carbon
atoms which may contain a halogen atom, and R.sup.18 and R.sup.19
optionally may be connected to each other to form a ring;
R.sup.24 represents a hydrocarbon group having from 1 to 5 carbon
atoms which may optionally contain a silicon atom;
R.sup.20 to R.sup.23, R.sup.25, and R.sup.26 are the same or
different and each represents a hydrogen atom or a hydrocarbon
group having from 1 to 20 carbon atoms which may optionally contain
silicon atom, R.sup.23 and R.sup.25, and optionally R.sup.24 and
R.sup.26 may be connected to each other via a carbon atom to form a
ring;
Y.sup.2 represents a carbon atom, a silicon atom, or a germanium
atom; and
n represents an integer of from 1 to 3, ##STR22## wherein M.sup.3
represents a transition metal atom selected from the group
consisting of Ti, Zr, and Hf;
X.sup.5 and X.sup.6 are the same or different and each represents a
hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to
20 carbon atoms which may contain halogen atom, an OR group, and SR
group, an OCOR group, an SO.sub.2 R group, an OSO.sub.2 R group, or
an NRR' group, in which R and R' are as defined above;
R.sup.27 and R.sup.28 are the same or different and each represents
a hydrogen atom, a hydrocarbon group having from 1 to 20 carbon
atoms, an OR group, or an SR group, in which R is as defined above,
and optionally R.sup.27 and R.sup.28 may be connected to each other
to form a ring;
R.sup.29 represents a hydrocarbon group having from 1 to 5 carbon
atoms which may optionally contain a silicon atom;
R.sup.30 and R.sup.31 are the same or different and each represents
a hydrogen atom or a hydrocarbon group having from 1 to 20 carbon
atoms which may optionally contain a silicon atom;
optionally R.sup.29 and R.sup.31 may be connected to each other via
a carbon atom to form a ring;
Y.sup.3 represents a carbon atom, a silicon atom, or a germanium
atom; and
n represents an integer of from 1 to 3.
11. A process for producing a polyolefin as claimed in claim 10,
wherein said catalyst further comprises (D) a particulate
carrier.
12. A process for producing a polyolefin as claimed in claim 10,
wherein R.sub.4 is a phenyl group, a tolyl group, a 2,6-dimethyl
phenyl group, a 2,4,6-trimethyl phenyl group, a naphthyl group or
an anthracenyl group.
13. A process for producing a polyolefin as claimed in claim 12,
wherein R.sub.4 is a phenyl group or a 1-naphthyl group.
14. A process for producing a polyolefin as claimed in claim 10,
wherein said process comprises polymerizing propylene.
Description
FIELD OF THE INVENTION
The present invention relates to a catalyst component for producing
polyolefin, a catalyst for producing polyolefin comprising the
catalyst component, and a process for producing polyolefin in the
presence of the catalyst. More particularly, the present invention
relates to a catalyst component capable of selectively polymerizing
(1) an ethylene polymer having a high melt tension, (2) an
ethylenic copolymer having a uniform comonomer distribution and (3)
a poly(.alpha.-olefin) elastomer, particularly polypropylene
elastomer and polymer containing it, depending on the kind of
olefin to be polymerized, a catalyst comprising the catalyst
component, and a process for producing polyolefin in the presence
of the catalyst component.
The polymer obtained according to the present invention can be
widely used in many fields, including automobile industry,
appliance industry, building industry and civil engineering and
construction industry.
BACKGROUND OF THE INVENTION
(1) Ethylenic polymer
It is known that an ethylenic polymer needs to have an enhanced
melt tension (MT) to enhance its moldability. To this end, studies
have been made of the enhancement of the melt tension of an
ethylenic polymer obtained by polymerization in the presence of a
Ziegler type titanium catalyst or Phillips type chromium catalyst.
For example, a method for the improvement of an ethylenic polymer
obtained by polymerization in the presence of a Ziegler type
catalyst which comprises the enhancement of its melt tension is
disclosed in JP-A-56-90810 and JP-A-60-106806 (The term "JP-A" as
used herein means an "unexamined published Japanese patent
application"). Although an ethylenic polymer obtained by
polymerization in the presence of a Ziegler type catalyst or
Phillips type catalyst can be improved in melt tension, it is
disadvantageous in that it has a broad molecular weight
distribution and hence a great content of low molecular weight
components which can be extracted with hexane, causing fuming
during forming.
An ethylenic polymer obtained by polymerization in the presence of
a metallocene catalyst system made of a metallocene compound and
methyl aluminoxane has a narrow molecular weight distribution and
has a small content of low molecular weight components, causing
less fuming during molding. However, such an ethylenic polymer
obtained by polymerization in the presence of a metallocene
catalyst system is disadvantageous in that it exhibits a low melt
tension and hence a poor moldability.
In order to solve the foregoing problem, a method for improving the
melt tension of polymers obtained by polymerization in the presence
of a metallocene catalyst system has been studied. For example,
JP-A-4-213306, JP-A-5-140224 and JP-A-5-140225 disclose a method
for producing an olefin polymer in the presence of a solid catalyst
comprising a crosslinked metallocene compound having a specific
structure and an organic aluminoxy compound. The use of such a
polymerization method provides an improvement in the melt tension
of the polymer (In the examples disclosed, when ethylenebisindenyl
zirconium compounds are used as metallocene compounds, remarkable
effects can be actually recognized). However, the systems disclosed
in these patents cannot provide polymers having a sufficient
molecular weight, making it difficult to control the molecular
weight of the resulting polymer by controlling the polymerization
conditions such as hydrogen content. In particular, it is difficult
to produce a polymer having a molecular weight as small as not more
than 0.1 in MFR (melt flow rate, JIS K-6301) equivalence. Thus,
this polymerization method can hardly be applied to multi-stage
polymerization. Further, the polymer thus obtained has an
insufficient molecular weight when used as a polyolefin
modifier.
Further, JP-A-5-345793 discloses the polymerization of ethylene in
the presence of a specific crosslinked indene-fluorene metallocene
compound. However, the polymer thus produced disadvantageously has
a low melt tension and a poor moldability as obtained by
polymerization in the presence of the conventional metallocene
compounds.
Thus, a method has been desired for producing a high molecular
weight ethylenic polymer having a high melt tension.
(2) Ethylenic copolymer
With respect to an ethylenic copolymers, it is known that the
molecular weight of the polymer and the comonomer composition
distribution in the polymer chain are important factors influencing
the properties of the polymer. In particular, high molecular weight
components having a uniform comonomer distribution has a great
effect on the improvement in the final properties (e.g., ESCR,
rigidity, impact resistance) of the product (JP-B-61-43378,
Macromol. Chem., Macromol. Symp., vol.41, p.55 (1991), J. Polym.
Sci.: Part B, vol. 29, p. 129 (1991)). (The term "JP-B" as used
herein means an "examined Japanese patent publication") In general,
an ethylenic copolymer produced by polymerization in the presence
of a Ziegler-Natta catalyst can maintain its properties because of
the presence of such a high molecular component. However, the
comonomer composition distribution in the polymer chain is
block-like, giving polymer with a higher degree of crystallization
that adversely affects the final product.
The use of a metallocene catalyst system provides a remarkable
improvement in the uniformity of the comonomer distribution in the
polymer chain. However, the use of a zirconocene/methyl aluminoxane
catalyst system which has early been developed cannot provide a
polymer with a sufficient molecular weight. An attempt to increase
the molecular weight of an ethylenic copolymer by improving the
metallocene compound in the metallocene catalyst system is
disclosed in U.S. Pat. No. 5,001,205, JP-A-5-148317, etc. However,
the metallocene catalyst systems disclosed therein leave something
to be desired in the molecular weight of the resulting polymer,
particularly taking into account the application as a high
molecular weight component for improving the foregoing final
properties of the product.
If a metallocene catalyst system can be proposed that enables the
production of a polymer with a higher molecular weight while
maintaining the uniformity of the comonomer composition
distribution in the polymer chain, it is of great industrial
value.
(3) Polypropylene elastomer
It has been known since first reported by Natta et al. that among
polypropylenes are those having elastic properties (polypropylene
elastomer).
U.S. Pat. No. 4,335,225, Macromolecules, vol. 22, p. 3851 (1989),
ibid, vol. 22, p. 3858 (1989), J. Polym. Sci. Part A:, vol. 27, p.
3063 (1989), JP-B-63-26122, JP-A-2-206608, JP-A-2-206633,and
JP-A-7-90010 propose polypropylene elastomer that which give a high
molecular weight atactic component in the component extracted with
diethyl ether and thus can exhibit elastomeric properties. However,
the catalyst system disclosed therein is a catalyst system having a
problem in that an alkyl complex of Ti or Zr supported on alumina
has a remarkably low activity.
In recent years, methods have been reported for the polymerization
of propylene in the presence of a metallocene catalyst system which
comprise direct polymerization to produce a polypropylene
elastomer. The elastomer obtained by polymerization in the presence
of this catalyst requires no separation process. Chien et al.
obtained a thermoplastic elastomer by the polymerization of
propylene in the presence of a crosslinked indene-cyclopentanediene
metallocene compound (British Patent 2241244, J. Am. Chem. Soc.,
vol. 112, p. 2030 (1990), Macromolecules, vol. 24, p. 850 (1991),
J. Am. Chem. Soc., vol. 113, p. 8569 (1991), Macromolecules, vol.
25, p. 7400 (1992), ibid, vol. 25, p. 1242 (1992), J. Polym. Sci.
Part A: vol. 30, p. 2601 (1992)). Waymouth et al. obtained a
thermoplastic elastomer polypropylene by the polymerization in the
presence of a non-crosslinked bisindene metallocene compound
(Science, vol. 267, p. 217 (1995)). However, these methods are
disadvantageous in that a polymer having a sufficient molecular
weight cannot be obtained at a practically effective polymerization
temperature. It is known that the elastomeric properties are
associated with the primary structure and molecular weight of the
polymer. The foregoing metallocene catalyst systems which cannot
provide a sufficient molecular weight impose a remarkable
restriction on the properties of the polymer.
A polymerization method is disclosed for producing a substantially
amorphous high molecular weight atactic polypropylene in the
presence of a crosslinked bislfluorene metallocene compound
(JP-A-6-234813, JP-A-6-256369) or monocyclopentanedienyl complex
(WO95/00562). It is also reported that the atactic polypropylene
thus obtained has elastomeric properties. However, the polymer thus
obtained disadvantageously exhibits a small tensile strength and
hence poor properties as an elastomer. Thus, the foregoing method
can hardly control the polymer properties by controlling the
polymerization conditions.
With respect to crosslinked indene-fluorene metallocene compounds,
a metallocene compound having unsubstituted indene ring and
fluorene ring is disclosed (JP-A-5-345793, Organometallics, vol.
13, p. 647 (1994)). However, polypropylenes thus produced have an
extremely low molecular weight and thus are obtained in the form of
oil or wax rather than thermoplastic elastomer.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a
metallocene catalyst system capable of selectively producing (1) a
high molecular ethylenic polymer having a high melt tension, (2) a
high molecular ethylenic copolymer having a uniform comonomer
composition distribution and (3) a poly(.alpha.-olefin) elastomer,
particularly polypropylene elastomer and polymer containing it,
depending on the kind of olefin to be polymerized.
The foregoing three polymers are keenly desirable in the industry.
If these polymers can be produced by using the same catalyst
system, it is extremely favorable from the standpoint of production
cost. It is also made possible to produce a high-performance resin
in a multi-stage polymerization process wherein a plurality of
polymers are produced in a single polymerization vessel.
Other objects and effects of the present invention will be apparent
from the following description.
The present inventors made extensive studies on the foregoing
problems. As a result, it was found that among crosslinked
metallocene compounds having indene ring and fluorene ring a
metallocene compound having specific substituents can be an
extremely excellent catalyst component that provides the solution
to the foregoing problems. Thus, the present invention has been
completed.
The present invention relates to, as a first aspect, a catalyst
component for producing polyolefin, the catalyst component
comprising a metallocene compound represented by formula (1):
##STR2## wherein M.sup.1 represents a transition metal atom
selected from Ti, Zr, and Hf;
X.sup.1 and X.sup.2 may be the same or different and each represent
a hydrogen atom, a halogen atom, a hydrocarbon group having from 1
to 20 carbon atoms which may contain a halogen atom, an OR group,
an SR group, an OCOR group, an SO.sub.2 R group, an OSO.sub.2 R
group, or an NRR' group, in which R and R' may be the same or
different and each represent a hydrogen atom or a hydrocarbon group
having from 1 to 7 carbon atoms which may contain a halogen
atom;
R.sup.1 and R.sup.2 may be the same or different and each represent
a hydrogen atom, a hydrocarbon group having from 1 to 20 carbon
atoms, an OR group, or an SR group, in which R represents a
hydrogen atom or a hydrocarbon group having from 1 to 7 carbon
atoms which may contain a halogen atom, R.sup.1 and R.sup.2 may be
connected to each other to form a ring;
R.sup.3 represents a hydrocarbon group having from 1 to 5 carbon
atoms which may contain a silicon atom;
R.sup.4 represents a hydrocarbon group having from 1 to 20 carbon
atoms which may contain a silicon atom;
R.sup.5 to R.sup.15 may be the same or different and each represent
a hydrogen atom or a hydrocarbon group having from 1 to 20 carbon
atoms which may contain a silicon atom, R.sup.5 to R.sup.15 may be
connected to each other to form a ring;
Y.sup.1 represents a carbon atom, a silicon atom, or a germanium
atom; and
n represents an integer of from 1 to 3.
In a preferred embodiments of the first embodiment of the present
invention, R.sup.3 represents a methyl group or an ethyl group; and
R.sup.4 represents a methyl group, an ethyl group, an n-propyl
group, an i-propyl group, or an aryl group having from 6 to 20
carbon atoms, or
R.sup.3 represents a methyl group or an ethyl group; R.sup.4
represents a phenyl group or a 1-naphthyl group; R.sup.5 to
R.sup.15 each represent a hydrogen atom; and n is 1.
The present invention also relates to, as a second aspect, a
catalyst for producing polyolefin, the catalyst comprising:
(A) the above catalyst component of the first aspect of the present
invention;
(B) a Lewis acid compound; and
(C) an organoaluminum compound.
In a preferred embodiment for the second aspect, the catalyst
further comprises (D) a particulate carrier.
The present invention further relates to, as a third aspect, a
process for producing a polyolefin, the process comprising the step
of homopolymerizing ethylene or copolymerizing ethylene and at
least one of olefin represented by formula (2):
wherein R.sup.16 and R.sup.17 may be the same or different and each
represents a hydrogen atom or a hydrocarbon group having from 1 to
14 carbon atoms other than ethylene, R.sup.16 and R.sup.17 may be
connected to each other to form a ring,in the presence of the
polyolefin production catalyst of the second aspect of the present
invention.
The present invention further relates to, as a fourth aspect, a
process for producing a polyolefin, said process comprising the
step of polymerizing one of olefin represented by formula (2) or
copolymerizing two or more of olefins represented by formula (2),
in the presence of a catalyst comprising:
(A) the above catalyst component of the first aspect of the present
invention;
(B) a Lewis acid compound; and
(C) an organoaluminum compound, or the catalyst comprising:
(A-1) the above catalyst component of the first aspect of the
present invention;
(A-2) an auxiliary metallocene compound for the polymerization of a
crystalline polyolefin;
(B) a Lewis acid compound; and
(C) an organoaluminum compound.
In a preferred embodiment for the fourth aspect, the catalyst
further comprises (D) a particulate carrier.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the relationship between the melt tension (MT) and the
melt flow rate (MFR) of ethylenic polymers in Examples and
Comparative Examples.
FIG. 2 shows the .sup.13 C--NMR spectrum in the methyl region of
the polypropylene produced under the conditions of Example 18.
FIG. 3 shows the .sup.13 C--NMR spectrum in the methyl region of
the polypropylene produced under the conditions of Example 22.
FIG. 4 shows the stress-stain curve of polypropylene produced under
the conditions of Example 18.
FIG. 5 shows the stress-stain curve of polypropylene produced under
the conditions of Example 22.
DETAILED DESCRIPTION OF THE INVENTION
The process for producing a polyolefin in the presence of a
catalyst for producing a polyolefin (hereinafter sometimes referred
to as olefin polymerization catalyst) according to the present
invention will be further described hereinafter.
The novel metallocene compound which is a first catalyst component
in the polymerization process of the present invention is
represented by formula (1). Formula (1) will be further described
hereinafter.
R.sup.3 represents a C.sub.1-5 hydrocarbon group which may contain
a silicon atom. Specific examples of such a C.sub.1-5 hydrocarbon
group include an alkyl group such as methyl, ethyl, n-propyl,
i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl and cyclopentyl; and
an alkylsilyl group such as trimethylsilyl. R.sup.3 is preferably
selected from the group consisting of methyl, ethyl, n-propyl and
i-propyl.
The expressions "C.sub.1-5 " and the like used herein means "having
from 1 to 5 carbon atoms" and the like.
R.sup.4 represents a C.sub.1-20 hydrocarbon group which may contain
a silicon atom. Specific examples of such a C.sub.1-20 hydrocarbon
group include an alkyl group such as methyl, ethyl, n-propyl,
i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, cyclopentyl,
cyclohexyl, octyl, nonyl and adamantyl, alkenyl group such as vinyl
and propenyl; an aryl group such as phenyl, tollyl,
2,6-dimethylphenyl, 2,4,6-trimethylphenyl, naphthyl and
anthracenyl; an arylalkyl group such as benzyl, phenylmethyl,
diphenylmethyl, triphenylmethyl and phenylethyl; an alkylsilyl
group such as methylsilyl, dimethylsilyl and trimethylsilyl; and a
silylalkyl group such as tris(trimethylsilyl)methyl. Preferred
among these hydrocarbon groups is one having a primary or secondary
carbon atom at the .alpha.-position, such as an alkyl group (e.g.,
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl) and an aryl
group (e.g., phenyl, tollyl, 2,6-dimethylphenyl,
2,4,6-trimethylphenyl, naphthyl, anthracenyl). Particularly
preferred among these hydrocarbon groups is an alkyl group such as
methyl, ethyl and i-propyl, and an aryl group such as phenyl and
1-naphthyl.
In the metallocene compound represented by formula (1) of the
present invention, it is important that both R.sup.3 and R.sup.4
are not a hydrogen atom and the indene ring has a hydrogen atom at
the 3-position. If R.sup.3 and R.sup.4 are a hydrogen atom at the
same time or the indene ring has no hydrogen atom at the
3-position, the effects of the present invention cannot be
exerted.
R.sup.5 to R.sup.15 may be the same or different and each represent
a hydrogen atom or a C.sub.1-20 hydrocarbon group which may contain
a silicon atom. In other words, R.sup.5 to R.sup.15 each represent
a hydrogen atom or has the same meaning as R.sup.4. R.sup.5 to
R.sup.15 may be connected to each other to form a ring. In
particular, neighboring groups are preferably connected to each
other to form an aromatic 6-membered ring. For example, it is
preferred that, in formula (1), the indene ring is 4,5-benzoindene,
5,6-benzoindene or 6,7-benzoindene, and the fluorene ring is
1,2-benzofluorene, 2,3-benzofluorene, 3,4-benzofluorene,
5,6-benzofluorene, 6,7-benzofluorene, 7,8-benzofluorene,
3,4,5,6-dibenzofluorene or 4,5-methylenephenanthrene. The indene
ring is particularly preferably 4,5-benzoindene.
X.sup.1 and X.sup.2 may be the same or different and each represent
a hydrogen atom, halogen atom, C.sub.1-20 hydrocarbon group which
may contain a halogen atom, an OR group, an SR group, an OCOR
group, an SO.sub.2 R group, an OSO.sub.2 R group, or an NRR' group
(in which R and R' may be the same or different and each represent
a hydrogen atom or a C.sub.1-7 hydrocarbon group which may contain
a halogen atom). For example, the halogen atom represents fluorine,
chlorine, bromine or iodine. The C.sub.1-20 hydrocarbon group which
may contain halogen atom may represent an alkyl group such as
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl,
n-pentyl, cyclopentyl and cyclohexyl; an alkenyl group such as
vinyl and propenyl; an aryl group such as phenyl, tollyl,
2,6-dimethylphenyl and 2,4,6-trimethylphenyl; an arylalkyl group
such as benzyl, phenylmethyl, diphenylmethyl, triphenylmethyl and
phenylethyl; a halogenated alkyl group such as trifluoromethyl; or
a halogenated aryl group such as pentafluorophenyl. The OR group
may represent a hydroxyl group; an alkoxy group such as methoxy,
ethoxy, propoxy and butoxy; or an aryloxy group such as phenoxy.
The SR group may represent a mercapto group; an alkylthio group
such as methylthio; or an arylthio group such as phenylthio. The
OCOR group may represent a carboxyl group or an alkoxycarbonyl
group such as methoxycarbonyl. The SO.sub.2 R group may represent a
sulfino group; an alkylsulfino group such as methylsulfino; or an
arylsulfino group such as phenylsulfino. The OSO.sub.2 R group may
represent a sulfo group; an alkylsulfo group such as methylsulfo;
or an arylsulfo group such as phenylsulfo and p-toluenesulfo. The
NRR' group may represent an amino group; an alkylamino group such
as methylamino, dimethylamino, diethylamino and dibutylamino; or an
arylamino group such as phenylamino. X.sup.1 and X.sup.2 are
preferably selected from a halogen atom and an alkyl group such as
methyl.
R.sup.1 and R.sup.2 may be the same or different and each represent
a hydrogen atom, a C.sub.1-20 hydrocarbon group, an OR group or an
SR group (in which R represents a hydrogen atom or a C.sub.1-7
hydrocarbon group which may contain a halogen atom). R.sup.1 and
R.sup.2 may be connected to each other to form a ring. For example,
the C.sub.1-20 hydrocarbon group may represent an alkyl group such
as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl,
n-pentyl, cyclopentyl and cyclohexyl; an alkenyl group such as
vinyl and propenyl; an aryl group such as phenyl, tollyl,
2,6-dimethylphenyl and 2,4,6-trimethylphenyl; or an arylalkyl group
such as benzyl, phenylmethyl, diphenylmethyl, triphenylmethyl and
phenylethyl. The OR group may represent a hydroxyl group; an alkoxy
group such as methoxy, ethoxy, propoxy and butoxy; or an aryloxy
group such as phenoxy. The SR group may represent a mercapto group;
an alkylthio group such as methylthio; or an arylthio group such as
phenylthio. R.sup.1 and R.sup.2 are preferably selected from
methyl, ethyl and phenyl.
Y.sup.1 represents a carbon atom, a silicon atom, or a germanium
atom.
In the crosslinking moiety represented by (R.sup.1 -Y.sup.1
-R.sup.2)n, n is preferably 1. R.sup.1 and R.sup.2 may be connected
to each other via Y.sup.1 to form a ring, and for example, a
1,1-cyclohexylidene ring is preferred.
Examples of the metallocene compound of the present invention
include:
Me.sub.2 Si[2-Me-4-(1-Naph)Ind](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-Et-4-(1-Naph)Ind](Flu)ZrCl.sub.2,
iPr[2-Me-4-(1-Naph)Ind](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-Me-4-PhInd](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-Et-4-PhInd](Flu)ZrCl.sub.21
iPr[2-Me-4-PhInd](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-Me-4-iPrInd](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-Et-4-iPrInd](Flu) ZrCl.sub.2,
iPr[2-Me-4-iPrInd](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-Me-4-EtInd](Flu) ZrCl.sub.2,
iPr[2-Me-4-EtInd](Flu)ZrCl.sub.2,
Me.sub.2 Si[2,4-Me.sub.2 Ind](Flu) ZrCl.sub.2,
iPr[2,4-Me.sub.2 Ind](Flu)ZrCl.sub.2,
Me.sub.2 Si[2,4,7-Me.sub.3 Ind](Flu)ZrCl.sub.2,
iPr[2,4,7-Me.sub.3 Ind](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-Me-4,6-iPr.sub.2 Ind](Flu)ZrCl.sub.2,
iPr[2-Me-4,6-iPr.sub.2 Ind](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-MeBenzind](Flu) ZrCl.sub.2,
iPr[2-MeBenzind](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-Me-4-(1-Naph)Ind](2,7-tBu.sub.2 Flu)ZrCl.sub.2,
iPr[2-Me-4-(1-Naph)Ind](2,7-tBu.sub.2 Flu)ZrCl.sub.2,
MePhSi[2-Me-4-(1-Naph)Ind](Flu)ZrCl.sub.2,
Ph.sub.2 Si[2-Me-4-(1-Naph)Ind](Flu)ZrCl.sub.2,
Me.sub.2 Ge[2-Me-4-(1-Naph)Ind](Flu)ZrCl.sub.2, and the
corresponding titanium and hafnium compounds.
Particularly preferred among these metallocene compounds are:
Me.sub.2 Si[2-Me-4-(1-Naph)Ind](Flu)ZrCl.sub.2,
iPr[2-Me-4-(1-Naph)Ind](Flu)ZrCl.sub.2,
Me.sub.2 Si[2-Me-4-PhInd](Flu)ZrCl.sub.2, and
iPr[2-Me-4-PhInd](Flu)ZrCl.sub.2.
In the foregoing formulae, Me represents a methyl group, Et
represents an ethyl group, iPr represents an isopropyl group, tBu
represents a t-butyl group, Ph represents a phenyl group, Naph
represents a naphthyl group, Ind represents an indenyl group,
Benzind represents a 4,5-benzoindenyl group, Flu represents a
fluorenyl group, Si[ ] represents a silylene group, iPr[ ]
represents an isopropylydene group, Ge[ ] represents a germylene
group, Zr represents a zirconium atom, and Cl represents a chlorine
atom.
The numerals indicating the position of substituents on the indene
ring and the fluorene ring in formula (1) are shown in formula (5).
##STR3##
The foregoing metallocene compounds of the present invention may be
used singly or in combination of two or more thereof.
Typical examples of the synthesis route of the metallocene compound
of the present invention will be outlined below, but the present
invention should not be construed as being limited thereto.
As the substituted indene to be used as a starting material,
commercial products may be used. Alternatively, such a substituted
indene can be synthesized by a known method. An example of the
synthesis method will be given below.
The substituted indene can be synthesized in accordance with the
synthesis method disclosed in Organometallics, vol. 13, p. 954
(1994): ##STR4##
As the substituted fluorene of formula (11), which is used as the
other starting material, commercial products may be used. If
necessary, the substituted fluorene can be synthesized by a known
technique: ##STR5##
An indenyl anion of formula (12): ##STR6## wherein M.sup.4
represents an alkaline metal atom such as lithium, sodium and
potassium, can be obtained by deprotonizing the substituted indene
(10) in a solvent in the presence of n-butyl lithium, sodium
hydride, potassium hydride or a strong base such as metallic sodium
and metallic potassium.
The indenyl anion (12) thus produced is then reacted with a
compound of formula (13): ##STR7## wherein X.sup.7 and X.sup.8 may
be the same or different and each represent a halogen atom, an OR
group, an SR group, an OCOR group, an OSO.sub.2 R group, or an NRR'
group (in which R and R' each represent a hydrogen atom or a
C.sub.1-7 hydrocarbon group) to obtain a compound of formula (14):
##STR8## The reaction is effected at a temperature of from
-78.degree. C. to 120.degree. C. in a molar ratio (12)/(13) of from
1/0.5 to 1/50, particularly from 1/1 to 1/20, with the substrate
concentration being from 0.1 mol/l to 10 mol/l. Preferred examples
of the reaction solvent employable herein include an aliphatic
hydrocarbon such as pentane, hexane and heptane; an aromatic
hydrocarbon such as benzene and toluene; and an ether such as
diethyl ether and tetrahydrofuran (THF).
The compound (14) thus produced and a fluorenyl anion of formula
(15): ##STR9## wherein M.sup.5 represents an alkaline metal atom
such as lithium, sodium and potassium, obtained by the
deprotonization of the substituted fluorene (11) in the presence of
the foregoing strong base, are reacted in a molar ratio (14)/(15)
of from 1/0.5 to 1/50, particularly from 1/1 to 1/20 to obtain a
compound of formula (16): ##STR10## The reaction is effected at a
temperature of from -78.degree. C. to 120.degree. C., particularly
from -20.degree. C. to 20.degree. C., with the substrate
concentration being from 0.1 mol/l to 10 mol/l. Preferred examples
of the reaction solvent employable herein include an aliphatic
hydrocarbon such as pentane, hexane and heptane; an aromatic
hydrocarbon such as benzene and toluene; and an ether such as
diethyl ether and tetrahydrofuran (THF).
The compound represented by formula (16), if n is 1 and Y.sup.1 is
a carbon atom, can be effectively synthesized by the following
method.
The substituted indene (10) and a ketone of formula (17): ##STR11##
are reacted to obtain a substituted benzofulvene of formula (18):
##STR12## For example, the substituted indene (10) is allowed to be
reacted with sodium ethoxide in ethanol, n-butyl lithium, sodium
hydride, potassium hydride or strong base such as metallic sodium
and metallic potassium, and then the ketone (17) is added in a
molar ratio (10)/(17) of from 1/0.5 to 1/50, particularly from 1/1
to 1/20.
The substituted benzofulvene (18) and the substituted fluorene (12)
are reacted in a molar ratio (18)/(12) of from 1/0.5 to 1/50,
particularly from 1/1 to 1/20 to obtain a compound of formula (19):
##STR13##
The compound (19) thus synthesized is then subjected to a method
known in references (J. Am. Chem. Soc., vol. 95, p. 6263 (1995),
Organometallics, vol. 14, p. 5 (1995)) to obtain a metallocene
compound.
For example, the compound (19) is deprotonized by the foregoing
strong base to obtain a dianion of formula (20): ##STR14## wherein
M.sup.6 represents an alkaline metal atom such as lithium, sodium
and potassium.
The compound (16) or the dianion (20) is then reacted with a
compound of formula (21):
wherein X.sup.1 and X.sup.2 may be the same or different and each
represent a halogen atom, an OR group, an SR group, an OCOR group,
an OSO.sub.2 R group or an NRR' group (in which R and R' may be the
same or different and each represent a hydrogen atom or a C.sub.1-7
hydrocarbon group); and n represents an integer of from 1 to 3, to
obtain a metallocene compound (1) (with the proviso that X.sup.1
and X.sup.2 are not an alkyl group). The reaction is effected at a
temperature of from -78.degree. C. to 120.degree. C., particularly
from -78.degree. C. to 30.degree. C., with the substrate
concentration being from 0.01 mol/l to 10 mol/l. Preferred examples
of the reaction solvent employable herein include an aliphatic
hydrocarbon such as pentane, hexane and heptane; an aromatic
hydrocarbon such as benzene and toluene; a halogenated hydrocarbon
such as dichloromethane; and an ether such as diethyl ether and
tetrahydrofuran (THF).
If X.sup.1 and X.sup.2 in formula (1) are hydrocarbon groups, the
compound (16) or the dianion (20) is acted upon by an alkylating
agent represented by formula (22):
wherein R.sup.32 represents a C.sub.1-20 hydrocarbon; and M.sup.7
represents an alkaline metal atom such as lithium, sodium and
potassium, to produce a metallocene compound represented by formula
(1).
The catalyst for producing a polyolefin according to the present
invention comprises (A) the catalyst component comprising the
metallocene compound of the present invention, (B) a Lewis acid
compound, and (C) an organoaluminum compound.
Examples of a Lewis acid compound as the second catalyst component
(B) can be roughly divided into the following two groups.
One of the two groups is an organic aluminoxy compound represented
by formula (23) or (24): ##STR15##
In formulae (23) and (24), R.sup.33, R.sup.34 and R.sup.35 may be
the same or different and each represent a hydrogen atom or a
C.sub.1-10 hydrocarbon group, preferably methyl, ethyl, n-propyl,
i-propyl, n-butyl or i-butyl, particularly preferably methyl or
i-butyl . The plurality of R.sup.36 groups may be the same or
different and each represent a C.sub.1-10 hydrocarbon group,
preferably methyl, ethyl, n-propyl, i-propyl, n-butyl or i-butyl,
particularly preferably methyl or i-butyl. The suffix n represents
an integer of from 1 to 100. Organic aluminoxy compounds
represented by formula (23) or (24) wherein n is from 3 to 100 are
preferably used in admixture. Alternatively, organic aluminoxy
compounds represented by formulae (23) an d (24) may be used in
admixture.
The preparation of these compounds can be accomplished by a known
method. Examples of such a known method include a method which
comprises the addition of a trialkyl aluminum to a suspension of a
salt having water of crystallization (e.g., hydrated copper
sulfate, hydrated aluminum sulfate) in a hydrocarbon solvent, and a
method which comprises allowing the foregoing suspension to be
acted upon by solid, liquid or gaseous water.
If n is 2 or more and the plurality of R.sup.36 groups are the
same, one trialkyl aluminum is used. If the plurality of R.sup.36
groups are different, two or more kinds of trialkyl aluminum or one
or more kinds of trialkyl aluminum and one or more kinds of dialkyl
aluminum monohydrides may be used. Specific examples of these
trialkyl aluminum and dialkyl aluminum monohydrides include a
trialkyl aluminum such as trimethyl aluminum, triethyl aluminum,
tri-n-propyl aluminum, tri-i-propyl aluminum, tri-n-butyl aluminum,
tri-i-butyl aluminum, tri-s-butyl aluminum, tri-t-butyl aluminum,
tripentylbutyl aluminum, trihexylbutyl aluminum and
tricyclohexylbutyl aluminum; a dialkyl aluminum halide such as
dimethyl aluminum chloride and di-i-butyl aluminum chloride; and a
dialkyl aluminum aryloxide such as dimethyl aluminum methoxide.
Preferred among these compounds is a trialkyl aluminum,
particularly preferably trimethyl aluminum or tri-i-butyl
aluminum.
The organic aluminoxy compound to be used in the present invention
may be further reacted with a compound having active hydrogen such
as water so that the organic aluminoxy compound of formula (23) or
(24) is crosslinked. Alternatively, the organic aluminoxy compound
to be used in the present invention may be a product of the
addition reaction with an organic polar compound having in its
molecule at least one atom selected from phosphorus, nitrogen,
sulfur and oxygen, and free of active hydrogen. The foregoing
organic aluminoxy compound may comprise an alcoholic additive or
the like incorporated therein to inhibit its aging. Examples of the
foregoing organic polar compound include trimethyl phosphate and
triethyl phosphate. In the presence of such an organic aluminoxy
compound, a polyolefin having excellent powder properties can be
produced without causing the polymer to be attached to the wall of
the polymerization vessel.
The other group of the second catalyst component is a Lewis acid
compound that reacts with a metallocene compound to produce an
ionic complex. Preferred examples of such a Lewis acid compound
include an organoboron compound, particularly an organoboron
compound having a pentafluorophenyl group, a
p-methyltetrafluorophenyl group, a p-t-butyltetrafluorophenyl group
or a p-trimethylsilyltetrafluorophenyl group. Specific examples of
such an organoboron compound include tri(pentafluorophenyl)boron,
tri(n-butyl)ammonium tetra(pentafluorophenyl)borate,
dimethylanilium tetra(pentafluorophenyl)borate, pyridinium tetra
(pentafluorophenyl)borate, ferrocenium tetra
(pentafluorophenyl)borate, triphenylcarbenium tetra
(pentafluorophenyl)borate, triphenylcarbenium tri
(pentafluorophenyl) (4-methyl-2,3,5,6-tetrafluorophenyl) borate,
triphenylcarbenium tri(pentafluorophenyl)
(4-t-butyl-2,3,5,6-tetrafluorophenyl)borate, and triphenylcarbenium
tri(pentafluorophenyl)
(4-trimethylsilyl-2,3,5,6-tetrafluorophenyl)borate.
The third catalyst component (C) to be used in the polymerization
process of the present invention is an organoaluminum compound. The
organoaluminum compound may be selected from a trialkyl aluminum
such as trimethyl aluminum, triethyl aluminum, tri-n-propyl
aluminum, tri-i-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl
aluminum, tri-s-butyl aluminum, tri-t-butyl aluminum, tripentyl
aluminum, trihexyl aluminum, trioctyl aluminum and tricyclohexyl
aluminum; a dialkyl aluminum halide such as dimethyl aluminum
chloride, diethyl aluminum chloride and di-i-butyl aluminum
chloride; a dialkyl aluminum alkoxide such as dimethyl aluminum
methoxide and diethyl aluminum ethoxide; a dialkyl aluminum
alkoxide such as dimethyl aluminum methoxide and diethyl aluminum
ethoxide; a dialkyl aluminum aryloxide such as diethyl aluminum
phenoxide; and an aluminoxane. Preferred among these organoaluminum
compounds is a trialkyl aluminum, particularly preferably trimethyl
aluminum, triethyl aluminum, tri-i-butyl aluminum, and trioctyl
aluminum. Such an organoaluminum compound may be replaced by an
organic aluminoxy compound represented by formula (23) or (24).
The catalyst for producing a polyolefin according to the present
invention may further be comprise (D) a particulate carrier.
The first, second and third catalyst components of the present
invention can be all supported on the particulate carrier (D)
(hereinafter singly referred to as "carrier") as the fourth
catalyst component. The particulate carrier employable herein
generally has an average particle diameter of from 10 to 300 .mu.m,
preferably from 20 to 200 .mu.m. The particulate carrier to be used
in the present invention is not specifically limited and can be
selected from organic and inorganic substances so far as it is
particulate and stays solid in the polymerization medium. If the
particulate carrier is an inorganic substance, it is preferably
selected from inorganic oxides, inorganic chlorides, inorganic
carbonate, inorganic sulfates and inorganic hydroxides. If the
particulate carrier is an organic substance, it is preferably from
organic polymers.
Examples of the inorganic substance include oxides such as silica
and alumina, chloride such as magnesium chloride, carbonate such as
magnesium carbonate and calcium carbonate, sulfates such as
magnesium sulfate and calcium sulfate, and hydroxide a such as
magnesium hydroxide and calcium hydroxide. Examples of the organic
substance include organic polymer carriers, and in particular, a
particulate polyethylene or polystyrene can be exemplified. The
particulate carrier is preferably selected from inorganic oxides,
particularly silica, alumina and a complex thereof.
Among these materials, a porous particulate carrier is preferred.
Such a porous particulate carrier is less attached to the inner
wall of the reaction vessel, making it possible to provide a
polymer having a higher bulk density. The porous particulate
carrier used in the present invention preferably has a specific
surface area of from 10 to 1,000 m.sup.2 /g, more preferably from
100 to 800 m.sup.2 /g, particularly preferably from 200 to 600
m.sup.2 /g. The pore volume of the porous particulate carrier is
preferably from 0.3 to 3 cc/g, more preferably from 0.5 to 2.5
cc/g, particularly preferably from 1.0 to 2.0 cc/g.
The particulate carrier can have different water adsorption and
surface hydroxyl group content with different treatment conditions.
The particulate carrier preferably has a water content of not more
than 5% by weight and a surface hydroxyl group content of not less
than 1/nm.sup.2 per surface area. The water content and surface
hydroxyl group content can be controlled by controlling the
calcining temperature or by treatment with an organoaluminum
compound or an organic boron compound. Further, a particulate
carrier which has been subjected to preliminary polymerization with
an olefin can also be used.
The polymerization catalyst of the present invention may further
comprise other components useful for the polymerization of olefin
besides the foregoing components.
Examples of the olefin to be polymerized in the process for
producing a polyolefin according to the present invention include
ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, cyclopentene,
cyclohexene, and styrene.
In the process of the present invention, it is preferred that
ethylene is homopolymerized or ethylene and at least one of olefin
represented by formula (2) are copolymerized:
wherein R.sup.16 and R.sup.17 may be the same or different and each
represents a hydrogen atom or a hydrocarbon group having from 1 to
14 carbon atoms other than ethylene, R.sup.16 and R.sup.17 may be
connected to each other to form a ring.
It is also preferred that one of olefin represented by formula (2)
is homopolymerized or two or more of olefins represented by formula
(2) are copolymerized.
Examples of the olefin represented by formula (2) to be polymerized
include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 3-methyl-1-butene, 4-methyl-l-pentene, cyclopentene,
cyclohexene, and styrene. Preferred examples of the olefin
represented by formula (2) to be copolymerized with ethylene
include propylene, 1-butene, 1-hexene, and 1-octene. Particularly
preferred among these olefins is propylene. In the polymerization
or copolymerization of one or more olefins represented by formula
(2), propylene is preferably homopolymerized, or alternatively,
propylene is preferably copolymerized with 1-butene or 1-hexene.
Particularly preferred among these polymers is propylene
homopolymer.
Further, a polyvalent unsaturated hydrocarbon can be polymerized.
Examples of the polyvalent unsaturated hydrocarbon to be
polymerized include a C.sub.5-80 polyvalent unsaturated hydrocarbon
with a molecular weight of not more than 1,100 having a plurality
of non-conjugated vinyl groups and at least two vinyl double bonds.
A particularly effective unsaturated hydrocarbon has from 8 to 20
carbon atoms. Specific examples of such a polyvalent unsaturated
hydrocarbon include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,
1,7-octadiene, 1,8-nonodiene, 1,9-decadiene, 1,13-tetradecadiene,
3-methyl-1,4-pentadiene, 4-methyl-1,5-hexadiene,
3-methyl-1,5-hexadiene, and 1,5,9-decatriene. Particularly
preferred among these are 1,5-hexadiene, 1,7-octadiene, and
1,9-decadiene. The proportion of the polyvalent unsaturated
hydrocarbon to be polymerized is preferably from 0.05 to 2% by
weight based on the amount of the olefin represented by formula
(2).
The time at which the first catalyst component (A) (catalyst
component comprising the metallocene compound of the present
invention) is brought into contact with the other catalyst
components (B) and (C) on the polymerization reaction may be
arbitrarily selected. For example, the first catalyst component (A)
and the second catalyst component (B) may be previously brought
into contact with each other (pre-contact), and then added to the
third catalyst component (C) and the olefin to be polymerized which
had been charged into the reaction vessel to initiate the
polymerization reaction. In an alternate method, the third catalyst
component (C) and the olefin to be polymerized may be charged into
the reaction vessel. The first catalyst component (A) and the
second catalyst component (B) may then be separately charged into
the reaction vessel to initiate the polymerization reaction. In
particular, if the second catalyst component (B) is an organic
aluminoxy compound represented by formula (23) or (24), the first
catalyst component (A) and the second catalyst component (B) can be
previously brought into contact with each other before being
supplied into the reaction system, to provide a remarkable
enhancement of polymerization activity.
The first, second and third catalyst components may be supported on
the fourth catalyst component (D) at any time as necessary. The
order of supporting these catalyst components on the fourth
catalyst component may be arbitrarily selected. Preferably, the
second catalyst component (B) may be mixed with the fourth catalyst
component (D) so that they are brought into contact with each other
. The first catalyst component (A) is then brought into contact
with the mixture. Alternatively, the first catalyst component (A)
and the second catalyst component (B) may be previously brought
into contact with each other. The fourth catalyst component (D) is
then mixed with the mixture so that they are brought into contact
with each other.
The above catalyst components may be mixed in a solvent such as an
aromatic hydrocarbon (e.g., benzene, toluene, xylene), an aliphatic
hydrocarbon (e.g., pentane, hexane, heptane, octane, decane), and
an alicyclic hydrocarbon (e.g., cyclopentane, cyclohexane) in the
presence or absence of olefin. The temperature at which these
components are mixed is generally from -70.degree. C. to
200.degree. C., preferably from -20.degree. C. to 120.degree. C.
The mixing time is generally from 1 to 600 minutes. When these
catalyst components are mixed, the first catalyst component (A) is
generally used in a concentration of from 10.sup.-6 to 10.sup.-3
mol per g of the fourth catalyst component (D).
The polymerization of the present invention can be accomplished by
any method known in the art such as solution polymerization, slurry
polymerization, gas phase polymerization, and high temperature melt
polymerization. The polymerization of the present invention may be
effected continuously or batchwise, and in one stage or a plurality
of stages.
The polymerization conditions are not specifically limited except
those specified in the process employed. The polymerization
temperature is generally from 0.degree. C. to 300.degree. C.,
preferably from 20.degree. C. to 150.degree. C., more preferably
from 40.degree. C. to 90.degree. C.
The concentration of the polyolefin polymerization catalyst
component used in the process of the present invention is not
particularly limited. The concentration of the metallocene compound
as the first catalyst component (A) is preferably from 10.sup.-10
to 10.sup.-3 mol/l with respect to the solvent or reaction vessel
volume. The concentration of the second catalyst component (B), if
it is an organic aluminoxy compound represented by formula (24) or
(25), is preferably from 10 to 10,000, particularly from 100 to
5,000 as calculated in terms of molar ratio of aluminum atom in the
organic aluminoxy compound to metallocene compound. The
concentration of the second catalyst component (B), if it is a
Lewis acid compound in the other group, such as an organoboron
compound, is preferably from 0.1 to 100, particularly from 0.2 to
10 as calculated in terms of molar ratio of Lewis acid compound to
metallocene compound. With respect to the third catalyst component
(C), the molar ratio of organoaluminum compound to metallocene
compound as first catalyst component (A) is generally from 10 to
100,000, preferably from 100 to 10,000 as calculated in terms of
aluminum atom in the organoaluminum compound.
The adjustment of the molecular weight of the resulting polymer can
be accomplished by any known method, e.g., by properly selecting
the polymerization temperature or introducing hydrogen into the
polymerization system.
The olefin polymerization catalyst of the present invention may be
used in combination with other olefin polymerization catalysts.
In the case where ethylene is polymerized or ethylene and one or
more olefins represented by formula (2) are copolymerized, the
metallocene compound of the present invention can be used in
combination with other known metallocene compounds to produce
ethylene polymers having different molecular weight
distributions.
In the case where one or more olefins represented by formula (2)
are polymerized or copolymerized, the metallocene compound of the
present invention can be used in combination with an auxiliary
metallocene compound for the polymerization of a crystalline
polyolefin, particularly crystalline polypropylene, to provide
further improvement in the elastic properties of the resulting
polymer.
Examples of the auxiliary metallocene compound for the
polymerization of a crystalline polypropylene to be used in the
present invention include compounds represented by formulae (3) and
(4): ##STR16## wherein M.sup.2 represents a transition metal atom
selected from Ti, Zr, and Hf; X.sup.3 and X.sup.4 may be the same
or different and each represent a hydrogen atom, a halogen atom, a
hydrocarbon group having from 1 to 20 carbon atoms which may
contain a halogen atom, an OR group, an SR group, an OCOR group, an
SO.sub.2 R group, an OSO.sub.2 R group, or an NRR' group, in which
R and R' may be the same or different and each represent a hydrogen
atom or a hydrocarbon group having from 1 to 7 carbon atoms which
may contain a halogen atom; R.sup.18 and R.sup.19 may be the same
or different and each represent a hydrogen atom, a hydrocarbon
group having from 1 to 20 carbon atoms, an OR group, or an SR
group, in which R represents a hydrogen atom or a hydrocarbon group
having from 1 to 7 carbon atoms which may contain a halogen atom,
R.sup.18 and R.sup.19 may be connected to each other to form a
ring; R.sup.24 represents a hydrocarbon group having from 1 to 5
carbon atoms which may contain silicon atom; R.sup.20 to R.sup.23,
R.sup.25, and R.sup.26 may be the same or different and each
represent a hydrogen atom or a hydrocarbon group having from 1 to
20 carbon atoms which may contain silicon atom, R.sup.23 and
R.sup.25, and R.sup.24 and R.sup.26 may be connected to each other
via a carbon atom to form a ring; Y.sup.2 represents a carbon atom,
a silicon atom, or a germanium atom; and n represents an integer of
from 1 to 3, ##STR17## wherein M.sup.3 represents a transition
metal atom selected from Ti, Zr, and Hf; X.sup.5 and X.sup.6 may be
the same or different and each represent a hydrogen atom, a halogen
atom, a hydrocarbon group having from 1 to 20 carbon atoms which
may contain halogen atom, an OR group, an SR group, an OCOR group,
an SO.sub.2 R group, an OSO.sub.2 R group, or an NRR' group, in
which R and R' are as defined above; R.sup.27 and R.sup.28 may be
the same or different and each represent a hydrogen atom, a
hydrocarbon group having from 1 to 20 carbon atoms, an OR group, or
an SR group, in which R is as defined above, R.sup.27 and R.sup.28
may be connected to each other to form a ring; R.sup.29 represents
a hydrocarbon group having from 1 to 5 carbon atoms which may
contain a silicon atom; R.sup.30 and R.sup.31 may be the same or
different and each represent a hydrogen atom or a hydrocarbon group
having from 1 to 20 carbon atoms which may contain a silicon atom;
R.sup.29 and R.sup.31 may be connected to each other via a carbon
atom to form a ring; Y.sup.3 represents a carbon atom, a silicon
atom, or a germanium atom; and n represents an integer of from 1 to
3.
For the details of the various substituents in formulae (3) and
(4), reference can be made to formula (1). However, the metallocene
compound represented by formula (3) or (4) is a metallocene
compound which is known to provide a crystalline polyolefin rather
than amorphous atactic polyolefin in the case of polymerization of
.alpha.-olefin such as propylene, among known metallocene
compounds.
Specific examples of the metallocene compound represented by
formula (3) include:
iPr[(Cp)(Flu)]ZrCl.sub.2,
iPr[3-tBuCp)(3-tBuInd)]ZrCl.sub.2, and
Me.sub.2 Si[(3-tBuCp) (Flu)]ZrCl.sub.2.
Specific examples of the metallocene compound represented by
formula (4) include:
Et[Ind].sub.2 ZrCl.sub.2,
Et[THInd].sub.2 ZrCl.sub.2,
Me.sub.2 Si[Ind].sub.2 ZrCl.sub.2,
Me.sub.2 Si[2-MeInd].sub.2 ZrCl.sub.2,
Me.sub.2 Si[2,4-Me.sub.2 Ind]2ZrCl2,
Me.sub.2 Si[2,4,7-Me.sub.3 Ind].sub.2 ZrCl.sub.2,
Me.sub.2 Si[2-Me-4,6-iPr.sub.2 Ind].sub.2 ZrCl.sub.2,
Me.sub.2 Si[2-Me-4-iPrInd].sub.2 ZrCl.sub.2,
Me.sub.2 Si[2-Me-4-PhInd].sub.2 ZrCl.sub.2,
Me.sub.2 Si[2-Me-4-(1-Naph)Ind].sub.2 ZrCl.sub.2,
Me.sub.2 Si[2-MeBenzind].sub.2 ZrCl.sub.2,
Me.sub.2 Si[3-tBucp].sub.2 ZrCl.sub.2,
Me.sub.2 Si[2-Me-4-tBuCp].sub.2 ZrCl.sub.2,
Me.sub.2 Si[2,4,5-Me.sub.3 Cp].sub.2 ZrCl.sub.2, and
Me.sub.2 Si[2,4,5-Me.sub.3 Cp].sub.2 HfCl.sub.2.
In the foregoing formulae, Me represents a methyl group, iPr
represents an isopropyl group, tBu represents a t-butyl group, Ph
represents a phenyl group, Naph represents a naphthyl group, Cp
represents a cyclopentadienyl group, Ind represents an indenyl
group, THInd represents a 4,5,6,7-tetrahydroindenyl group, Benzind
represents a 4,5-benzoindenyl group, Flu represents a fluorenyl
group, Si[ ] represents a silylene group, iPr[ ] represents an
isopropylydene group, Et[ ] represents an ethylidene group, Zr
represents a zirconium atom, Hf represents a hafnium atom, and Cl
represents a chlorine atom.
The metallocene compounds exemplified above are all known from
JP-A-3-314978, JP-A-6-122718, U.S. Pat. No. 5,132,262, Angew. Chem.
Int. Ed. Enql., vol. 24, p. 507 (1985), J. Am. Chem. Soc., vol.
110, p. 6255 (1998), Chem. Lett., p. 1853 (1989), Orqanometallics,
vol. 13, p. 954 (1994), ibid vol. 13, p. 964 (1994)
In the procedure of synthesis of the metallocene compound
represented by formula (1) of the present invention, a metallocene
compound (3) or (4) for the polymerization of a crystalline
polyolefin, particularly crystalline polypropylene, may be
simultaneously synthesized. The two metallocene compounds thus
synthesized may be used for polymerization without being isolated.
The metallocene catalyst system comprising a metallocene compound
represented by formula (1) may be used in combination with other
crystalline polyolefin production catalyst which has heretofore
been known, e.g., magnesium chloride-supported Ziegler-Natta
catalyst, than the foregoing crystalline polyolefin production
metallocene catalyst system.
The polyolefin obtained in the present invention can be used as a
modifier or compounding agent for various resins.
The polyolefin obtained by the polymerization of ethylene or the
copolymerization of ethylene with one or more olefins represented
by formula (2) can be blended with other polyolefins to enhance its
moldability or the properties of the final product.
The polyolefin obtained by the polymerization or copolymerization
of one or more olefins represented by formula (2) exhibits
excellent properties if blended with other poly(.alpha.-olefin).
For example, the polyolefin of the present invention can exhibit
enhanced elastic properties when blended with, e.g., a crystalline
poly(.alpha.-olefin) as crystalline poly(.alpha.-olefin) having a
stereoregularity of mm % .gtoreq.90% or rr % .gtoreq.80% in an
amount of not more than 50% by weight. Further, such a crystalline
poly(.alpha.-olefin) can exhibit a drastic enhancement of impact
resistance if blended with the polyolefin of the present invention
in an amount of not more than 50% by weight. In particular, an
isotactic polypropylene resin which requires a high impact
resistance when used as an automobile bumper or the like can be
blended with the polyolefin of the present invention, particularly
polypropylene polymer to advantage. Further, the polyolefin of the
present invention obtained by the polymerization or
copolymerization of one or more olefins represented by formula (2)
is essentially amorphous and thus can be a compounding agent
extremely excellent in radiation resistance.
The polyolefin obtained in the present invention can make the best
use of its transparency, flexibility, strength, formability,
heat-sealability or other properties so that it can be incorporated
in various products.
The polyolefin obtained in the present invention can also be used
as a modifier or compounding agent for resins other than the
foregoing crystalline polyolefin, such as an ethylene-vinyl acetate
copolymer, a saponification product thereof, an ethylene-vinyl
alcohol copolymer, a halogen-containing copolymer (e.g.,
polyvinylidene chloride, polyvinyl chloride, polyvinyl fluoride,
polyvinylidene fluoride, polypropylene, rubber chloride), an
unsaturated carboxylic acid, and a polymer of derivatives thereof
(e.g., polymethyl methacrylate, polyalkyl acrylate).
The polyolefin obtained in the present invention can be further
used as a starting material of various graft copolymers and block
copolymers.
The present invention will be further described in the following
examples, but the present invention should not be construed as
being limited thereto.
In the examples below, the metallocene compound of the present
invention was identified by the following methods.
.sup.1 H-NMR:
.sup.1 H-NMR of the metallocene compound was measured in
chloroform-d at a temperature of 30.degree. C.
Mass spectrometry:
The specimen was introduced by a direct introduction method, and
then ionized by an electron bombardment method (70 eV) for
measurement.
The physical properties of the polymer were measured as
follows:
.sup.13 C--NMR:
.sup.13 C--NMR of the polymer was measured in a 1:3 mixture (by
weight) of benzene-d.sub.6 and 1,3,5-trichlorobenzene at a
temperature of 120.degree. C. (measurement mode: proton decoupling
method; pulse width: 8.0 .mu.s; pulse repetition time: 3.0 s;
integrating time: 20,000; internal standard: hexamethyl
disiloxane).
The reactivity ratio r.sub.1 r.sub.2, which indicates the comonomer
composition distribution in the ethylenic copolymer, and the extent
of incorporated comonomer in the polymer chain are calculated in
accordance with J. Polm. Sci., Polym. Chem., vol. 29, p. 1585
(1991), Polym. Bull., vol. 26, p. 325 (1991).
The stereoregularity of the polypropylene was evaluated by the
intensity ratio of mm, mr and rr signals derived from methyl group
in accordance with Macrolecules, vol. 6, p. 925 (1973), ibid, vol.
8, p. 687 (1975).
Gel permeation chromatography (GPC):
The gel permeation chromatography of the polymer was effected in
1,2,4-trichlorobenzene at a column temperature of 135.degree. C.
and a solvent flow rate of 1 ml/min.
Differential scanning calorimetry (DSC):
The polymer was heated to a temperature of 230.degree. C. where it
was then kept for 5 minutes. The polymer thus heated was then
scanned while being cooled at a rate of 20.degree. C./min. for the
measurement of heat of crystallization. The polymer was then kept
at a temperature of 25.degree. C. for 5 minutes. The polymer was
then scanned while being heated at a rate of 20.degree. C./min. for
the measurement of heat of fusion.
The ethylenic polymer was measured for the following
properties:
Melt flow rate (MFR):
The melt flow rate of the ethylenic polymer was measured at a
temperature of 190.degree. C. under a load of 2.16 kg in accordance
with JIS K-6760.
High load melt flow rate (HLMFR):
The high load melt flow rate of the ethylenic polymer was measured
at a temperature of 190.degree. C. under a load of 21.6 kg in
accordance with JIS K-6760.
Density:
The density of the ethylenic polymer was measured in accordance
with JIS K-6750. Specifically, the specimen was pressed at
temperatures of 23.degree. C. and 190.degree. C., cut, deaerated in
ethanol, and then measured by means of a density gradient tube.
Melt tension (MT):
The polymer specimen to be measured was in the form of powder. The
measurement was effected with an orifice inner diameter of 2.095
.+-.0.005 mm and an orifice length of 8.000.+-.0.025 mm at a resin
temperature of 190.degree. C., an extrusion speed of 15 mm/min. and
a winding speed of 6.5 m/min.
The propylene polymer was measured for the following
properties:
Tensile test:
The tensile test was conducted in accordance with JIS K-6301.
Specifically, the propylene polymer was kneaded at a temperature of
230.degree. C. by means of a 3-in. roll for 5 minutes, and then
pressed into a 1-mm thick plate to obtain a No. 2 1/2 dumbbell
specimen. The measurement was conducted at a pulling speed of 200
mm/min.
Elongation set:
A specimen having 20 mm between two gage marks was kept extended by
100% for 1 minute. When 10 minutes passed since the specimen was
released, the distance D between the two gage marks was measured.
The elongation set was calculated from the following equation:
Internal haze:
A 0.5-mm thick pressed plate was measured for internal haze in
accordance with JIS K7105.
The analyzers used for the measurement of physical properties are
as follows:
NMR: EX-400 (available from Nihon Denshi K. K.)
Mass spectrometry: AX-500 (available from Nihon Denshi K. K.)
GPC: Waters 150C (Shodex; GPC AT-806MS column)
DSC: Perkin Elmer DSC7
MT: Melt Tension Tester II (available from Toyo Seiki Seisakujo K.
K.)
Among known metallocene compounds, the following compounds were
synthesized in accordance with known references.
JP-A-5-345793:
Isopropylidene(1-indenyl)(9-fluorenyl)zirconium dichloride
JP-A-63-235309:
Bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride
J. Organomet. Chem., vol. 288, p. 63 (1985):
rac-Ethylidenebis(indenyl) zirconium dichloride
U.S. Pat. No. 5,001,205:
rac-Dimethylsilylenebis(tetrahydroindenyl) zirconium dichloride
Organometallics, vol. 13, p. 954 (1994):
rac-Dimethylsilylenebis(2-methyl-4-(1-naphthyl) indenyl)-zirconium
dichloride
Isopropylidene(3-t-butyl-l-indenyl)(9-fluorenyl)-zirconium
dichloride used in Comparative Example 16 was synthesized in the
same manner as in Examples 1 and 2. Synthesis of Metallocene
Compound:
EXAMPLE 1
Synthesis of Dimethylsilylene(2-methyl-4-(1-naphthyl)Indenyl)
(9-Fluorenyl Zirconium Dichloride (IMNFZ)
(1) Dimethyl(2-methyl-7-(1-naphthyl)indenyl) (9-fluorenyl)silane
was synthesized.
The reaction was effected in an atmosphere of nitrogen gas. The
glass reaction vessel used had been previously dried. 5.0 g (19.5
mmol) of 2-methyl-7-(1-naphthyl)indene (synthesized in accordance
with Organometallics, vol. 13, p. 954 (1994)) was dissolved in 100
ml of dried tetrahydrofuran (THF). To the solution was then added
13.0 ml (20.8 mmol) of a 1.6 mol/l hexane solution of n-butyl
lithium over ice-water bath. The reaction mixture was then allowed
to undergo reaction at room temperature for 3 hours to obtain a
light brown solution. A solution of 2.7 g (21 mmol) of dimethyl
dichlorosilane in 200 ml of THF was cooled to a temperature of
0.degree. C. To the solution was then added dropwise the light
brown solution which had been previously prepared in 2 hours. After
the completion of the dropwise addition, the temperature of the
mixture was returned to room temperature where it was then stirred
for 12 hours. To the solution was then added dropwise a fluorenyl
lithium solution which had been similarly prepared from 3.32 g (20
mmol) of fluorene and 13.0 ml of a n-butyl lithium solution while
being cooled with ice over 15 minutes. The temperature of the
mixture was returned to room temperature where it was then stirred
for 12 hours. The reaction solution was stirred with an aqueous
solution of ammonium chloride, extracted with 500 ml of diethyl
ether, and then dried over anhydrous sodium sulfate. The material
was then subjected to column chromatography (silica gel; developing
solvent: n-hexane) to separate the reaction product from the
starting materials. As a result, 5.6 g (11.7 mmol; yield: 59%) of
the desired compound was obtained.
The elementary analysis of the compound thus obtained is given
below.
Elementary analysis: Calculated (%) for C.sub.35 H.sub.30 Si:
C87.82, H6.32; Found (%): C87.95, H6.55
(2) The subsequent reaction of synthesis to zirconium complex was
effected in an atmosphere of argon gas. 6.5 g (13.6 mmol) of
dimethyl(2-methyl-7-(l-naphthyl)indenyl)-(9-fluorenyl)silane thus
obtained was dissolved in 100 ml of dried THF. To the solution was
then added 18.7 ml (28.7 mmol) of a 1.65 mol/l hexane solution of
n-butyl lithium while being cooled with ice. The reaction mixture
was then allowed to undergo reaction at room temperature for 2
hours. THF was then distilled off under reduced pressure. To the
solution was then added 50 ml of dried toluene while being cooled
to a temperature of -78.degree. C. to obtain a greenish brown
suspension. 3.2 g (13.6 mmol) of zirconium tetrachloride was
suspended in 100 ml of dried toluene in a flask. The suspension was
then cooled to a -78.degree. C. Under these conditions, the
greenish brown toluene solution which had been previously prepared
was then added to the suspension through a cannula while being
cooled to the same temperature. The reaction mixture was then
stirred at a temperature of -78.degree. C. for 1 hour. The
temperature of the mixture was returned to room temperature where
it was then allowed to undergo reaction for 10 hours to obtain a
red suspension. The suspension was then subjected to centrifugal
separation to remove the toluene solution and separate a red solid
therefrom. The red solid thus obtained was then extracted with 600
ml of dried methylene chloride by means of a Soxhlet extractor. The
resulting red transparent solution was then concentrated to
precipitate a red crystal.
Mass spectrometry: EI (70 eV), direct introduction method, 638
(M.sup.+); .sup.1 H-NMR (400 MHz, CDCl.sub.3): .delta.1.43 (3H,
Si--CH.sub.3), 1.60 (3H, Si--CH.sub.3), 2.17 (3H, Ind--CH.sub.3),
6.25 (1H, Ind--H), 6.9-8.4 (18H, Aryl-H)
Elementary analysis: Calculated (%) for C.sub.35 H.sub.28
SiZrCl.sub.2 : C65.81, H4.42; Found (%): C64.20, H3.91
EXAMPLE 2
Synthesis of Dimethylsilylene(2-methyl-4-phenylindenyl)
(9-fluorenyl)Zirconium Dichloride (IMPFZ)
(1) Dimethyl(2-methyl-7-phenylindenyl) (9-fluorenyl)silane was
synthesized.
The procedure of Example 1 was followed. In some detail, 6.3 g
(30.5 mmol) of 2-methyl-7-phenylindene (synthesized in accordance
with Organometallics, vol. 13, p. 954 (1994)) was dissolved in 100
ml of dried tetrahydrofuran (THF). To the solution was then added
21.0 ml (33.6 mmol) of a 1.6 mol/l hexane solution of n-butyl
lithium over ice-water bath. The reaction mixture was then allowed
to undergo reaction at room temperature for 3 hours. The solution
was then added dropwise to a solution of 4.4 g (34 mmol) of
dimethyl dichlorosilane in 200 ml of THF over ice-water bath over 2
hours. After the completion of the dropwise addition, the
temperature of the mixture was returned to room temperature where
it was then stirred for 12 hours. To the solution was then added
dropwise a fluorenyl lithium solution which had been similarly
prepared from 5.1 g (30.5 mmol) of fluorene and 21.0 ml of a
n-butyl lithium solution while being cooled with ice in 15 minutes.
The temperature of the mixture was returned to room temperature
where it was then stirred for 12 hours. The reaction solution was
stirred with an aqueous solution of ammonium chloride, extracted
with diethyl ether, and then dried over anhydrous sodium sulfate.
The material was then subjected to column chromatography (silica
gel; developing solvent: n-hexane) to separate the reaction product
from the starting materials. As a result, 8.5 g (19.8 mmol; yield:
65%) of the desired compound was obtained.
The elementary analysis of the compound thus obtained is given
below.
Elementary analysis: Calculated (%) for C.sub.31 H.sub.28 Si:
C86.92, H6.54; Found (%): C86.95, H6.75
(2) The subsequent reaction of synthesis to zirconium complex was
effected in the same manner as in Example 1. In some detail, 6.8 g
(15.9 mmol) of
dimethyl(2-methyl-7-phenylindenyl)(9-fluorenyl)silane thus obtained
was dissolved in 100 ml of dried THF. To the solution was then
added 21.8 ml (35.0 mmol) of a 1.65 mol/l hexane solution of
n-butyl lithium while being cooled with ice. The reaction mixture
was then allowed to undergo reaction at room temperature for 2
hours. THF was then distilled off under reduced pressure. To the
solution was then added 50 ml of dried toluene while being cooled
to a temperature of -78.degree. C. to obtain a greenish brown
suspension. On the other hand, 3.7 g (15.9 mmol) of zirconium
tetrachloride was suspended in 100 ml of dried toluene in a flask.
The suspension was then cooled to a -78.degree. C. Under these
conditions, the greenish brown toluene solution which had been
previously prepared was then added to the suspension through a
cannula while being cooled to the same temperature. The reaction
mixture was then stirred at a temperature of -78.degree. C. for 1
hour. The temperature of the mixture was returned to room
temperature where it was then allowed to undergo reaction for 10
hours to obtain a red suspension. The suspension was then subjected
to centrifugal separation to remove the toluene solution and
separate a red solid therefrom. The red solid thus obtained was
then extracted with dried methylene chloride by means of a Soxhlet
extractor. A red crystal was then obtained from the resulting red
transparent solution.
Mass spectrometry: EI (70 eV), direct introduction method, 588
(M.sup.+); .sup.1 H-NMR (400 MHz, CDCl.sub.3): .delta.1.43 (3H,
Si--CH.sub.3), 1.60 (3H, Si--CH.sub.3), 2.21 (3H, Ind--CH.sub.3),
6.40 (1H, Ind--H), 6.9-8.4 (18H, Aryl-H)
Elementary analysis:
Calculated (%) for C.sub.31 H.sub.26 SiZrCl.sub.2 : C63.27, H4.42;
Found (%): C63.20, H4.20
Preparation of Ethylenic Polymer:
EXAMPLE 3
Supporting of methylaluminoxane on carrier
Into a 100-ml flask the air in which had been thoroughly replaced
by nitrogen were charged 25 ml of toluene and 1.5 g of silica
(obtained by calcining Davison 952 at a temperature of 300.degree.
C. for 4 hours). To the suspension thus obtained was then added 37
ml of methylaluminoxane (1.35 mol/l (in aluminum atom equivalence)
toluene solution, available from Toso Aczo Co., Ltd.). The reaction
mixture was then stirred at room temperature for 30 minutes. The
solvent was then distilled off under reduced pressure. To the
reside was then added 50 ml of heptane. The reaction mixture was
then stirred at a temperature of 80.degree. C. for 4 hours. The
reaction solution was then washed with heptane twice at a
temperature of 80.degree. C. to obtain a solid component. The solid
component comprised methylaluminoxe in an amount of 33% by
weight.
Polymerization
Into a 1.5-l internal volume SUS autoclave the air in which had
been thoroughly replaced by nitrogen were introduced 3.2 ml of a
0.5 mol/l hexane solution of tri-i-butyl aluminum, 105 mg of the
foregoing silica-supported methylaluminoxane, a solution of 2.02 mg
of dimethylsilylene(2-methyl-4-(1-naphthyl)
indenyl)-(9-fluorenyl)zirconium dichloride (IMNFZ) synthesized in
Example 1 in 6 ml of toluene, and 800 ml of isobutane. The reaction
mixture was then heated to a temperature of 70.degree. C. Into the
reaction system was then introduced ethylene to initiate
polymerization. The polymerization was effected at an ethylene
pressure of 10 kg/cm.sup.2 and a temperature of 70.degree. C. for
30 minutes to obtain 69.3 g of a polymer. The polymer exhibited an
activity of 6.9 kg-polymer/g-complex.multidot.hr.multidot.atm.
The physical properties of the polymer thus obtained were as
follows:
Mw=990,000; Mw/Mn=4.25
The polymer exhibited a density of 0.948 g/cm.sup.3 and a melting
point of 132.degree. C. The melt tension of the polymer was
immeasurable.
EXAMPLE 4
Into a 1.5-l internal volume SUS autoclave the air in which had
been thoroughly replaced by nitrogen were introduced 3.2 ml of a
0.5 mol/l hexane solution of triisobutyl aluminum, 105 mg of the
silica-supported methylaluminoxane prepared in Example 3, a
solution of 2.02 mg of dimethylsilylene(2-methyl-4-(1-naphthyl)
indenyl)-(9-fluorenyl)zirconium dichloride (IMNFZ) synthesized in
Example 1 in 6 ml of toluene, and 800 ml of isobutane. The reaction
mixture was then heated to a temperature of 70.degree. C. Into the
reaction system was then introduced a mixture (H.sub.2 /C.sub.2 (by
weight)=4.times.10.sup.-5) of ethylene and hydrogen to initiate
polymerization. The polymerization was effected at a mixture gas
pressure of 10 kg/cm.sup.2 and a temperature of 70.degree. C. for
30 minutes to obtain 37.6 g of a polymer. The polymer exhibited an
activity of 3.7 kg-polymer/g-complex.multidot.hr.multidot.atm.
The physical properties of the polymer thus obtained were as
follows:
HLMFR=0.11; Mw=407,000; Mw/Mn=3.94
The polymer exhibited a density of 0.957 g/cm.sup.3 and a melting
point of 132.degree. C. The melt tension of the polymer was
immeasurable.
EXAMPLES 5 TO 7
Polymerization was effected in the same manner as in Example 4
except that the mixing gas ratio was altered. The polymerization
conditions and results are set forth in Table 1. The physical
properties of the polymer thus obtained are set forth in Table
2.
EXAMPLES 8 TO 10
Polymerization was effected in the same manner as in Examples 3 to
7 except that dimethylsilylene(2-methyl-4-phenylindenyl)
(9-fluorenyl)zirconium dichloride (IMPFZ) produced in Example 2 was
used as a metallocene compound. The polymerization conditions and
results are set forth in Table 1. The physical properties of the
polymer thus obtained are set forth in Table 2.
COMPARATIVE EXAMPLE 1
Polymerization was effected in the same manner as in Example 3
except that isopropylidene(indenyl)(fluorenyl)-zirconium dichloride
(a) was used as a metallocene compound. The polymerization
conditions and results are set forth in Table 1. The physical
properties of the polymer thus obtained are set forth in Table
2.
COMPARATIVE EXAMPLES 2 AND 3
Polymerization was effected in the same manner as in Examples 3 and
4 except that bis(n-butylcyclopentadienyl)-zirconium dichloride (b)
was used as a metallocene compound. The polymerization conditions
and results are set forth in Table 1. The physical properties of
the polymer thus obtained are set forth in Table 2.
COMPARATIVE EXAMPLES 4 AND 5
Polymerization was effected in the same manner as in Examples 3 and
4 except that bis(1-methyl-3-n-butylcyclopentadienyl) zirconium
dichloride (c) was used as a metallocene compound. The
polymerization conditions and results are set forth in Table 1. The
physical properties of the polymer thus obtained are set forth in
Table 2.
COMPARATIVE EXAMPLE 6
Polymerization was effected in the same manner as in Example 4
except that bis(1,2,4-trimethylcyclopentadienyl)-zirconium
dichloride (d) was used as a metallocene compound. The
polymerization conditions and results are set forth in Table 1. The
physical properties of the polymer thus obtained are set forth in
Table 2.
COMPARATIVE EXAMPLES 7 AND 8
Polymerization was effected in the same manner as in Examples 3 to
5 except that ethylidenebis(indenyl)zirconium dichloride (e) was
used as a metallocene compound. The polymerization conditions and
results are set forth in Table 1. The physical properties of the
polymer thus obtained are set forth in Table 2.
The relationship between MT and MFR was determined from these
results as shown in FIG. 1.
The comparison of the foregoing examples with the comparative
examples shows that the metallocene compound of the present
invention can form a catalyst enabling the production of a
polyethylene having a high melt tension. In particular, the
comparison of the examples with Comparative Example 1 shows that
among crosslinked metallocene compound groups having indene ring
and fluorene ring, the group having substituents of the present
invention can form a catalyst enabling the production of a
polyethylene having a specifically high melt tension.
Further, the comparison of the examples with Comparative Examples 7
and 8 shows that the metallocene compound of the present invention
enables the production of a polyethylene having a higher molecular
weight than the metallocene compounds which have heretofore been
known to form catalysts enabling the production of a polyethylene
having a high melt tension even if hydrogen is introduced into the
polymerization system during the polymerization.
TABLE 1
__________________________________________________________________________
Ethylene Hydrogen Weight MAO/SiO.sub.2 TIBA pressure ratio Yield
Activity Metallocene (mg) (mg) (ml) (Kg/cm.sup.2) (10.sup.-5 wt %)
(g) (Kg-PE/g-Zr .multidot. h .multidot. atm)
__________________________________________________________________________
Example 3 IMNFZ 2.02 105 3.2 10 0.0 49 4.9 Example 4 IMNFZ 2.02 105
3.2 10 4.2 38 3.7 Example 5 IMNFZ 2.02 105 3.2 10 8.2 28 2.8
Example 6 IMNFZ 2.02 105 3.2 10 17.3 21 2.0 Example 7 IMNFZ 2.02
105 3.2 10 25.5 15 1.4 Example 8 IMPFZ 2.71 151 4.6 10 0.0 86 8.4
Example 9 IMPFZ 2.82 158 4.8 10 17.3 59 4.2 Example 10 IMPFZ 3.19
179 5.4 10 23.0 63 4.0 Comparative a 2.73 187 5.7 10 0.0 21 1.6
Example 1 Comparative b 2.42 197 6.0 10 0.0 105 8.7 Example 2
Comparative b 2.29 187 5.7 10 4.2 75 6.5 Exampie 3 Comparative c
2.19 167 5.1 10 0.0 105 10.9 Example 4 Comparative c 2.10 158 4.8
10 4.2 87 8.3 Example 5 Comparative d 3.31 289 8.8 10 4.2 22 1.3
Example 6 Comparative e 3.12 246 7.5 10 0.0 57 3.7 Example 7
Comparative e 3.12 246 7.5 10 7.1 41 2.6 Example 8
__________________________________________________________________________
TABLE 2
__________________________________________________________________________
MFR HLMFR Mw Density Tm Melt tension (g/10 min) (g/10 min)
(.times.10.sup.-3) Mw/Mn (g/cm.sup.3) (.degree.C.) (g)
__________________________________________________________________________
Example 3 -- -- 990 4.61 0.948 132 -- Example 4 -- 0.11 407 3.94
0.957 132 -- Example 5 0.01 1.21 279 4.61 0.939 132 -- Example 6
0.08 2.85 211 4.25 0.950 133 31.0 Example 7 1.83 61.5 95 3.37 0.945
133 10.5 Example 8 -- -- 870 3.75 0.951 133 -- Example 9 0.07 2.73
225 3.91 0.953 133 32.3 Example 10 1.95 60.5 90 3.85 0.949 133 10.0
Comparative 0.08 3.05 180 2.64 0.950 134 5.1 Example 1 Comparative
0.09 3.15 175 2.29 0.939 131 4.5 Example 2 Comparative 4.78 90.6 72
2.23 0.930 132 0.1 Example 3 Comparative 0.07 2.79 195 2.73 0.939
131 4.7 Example 4 Comparative 2.17 73 85 2.55 0.943 132 0.6 Example
5 Comparative 0.32 11.3 157 2.43 0.935 131 3.0 Example 6
Comparative 0.06 2.98 170 3.57 0.951 134 26.8 Example 7 Comparative
2.02 60.1 80 3.59 0.946 132 8.3 Example 8
__________________________________________________________________________
Preparation of Ethylenic Copolymer:
EXAMPLE 11
Into a 1.5-l internal volume SUS autoclave the air in which had
been thoroughly replaced by nitrogen were introduced 1.1 ml of a
0.5 mol/l hexane solution of tri-i-butyl aluminum, 36 mg of the
foregoing silica-supported methylaluminoxane, a solution of 0.69 mg
of dimethylsilylene(2-methyl-4-(1-naphthyl)indenyl)(9-fluorenyl)
zirconium dichloride (IMNFZ) synthesized in Example 1 in 6 ml of
toluene, and 800 ml of 1-hexene. The reaction mixture was then
heated to a temperature of 70.degree. C. Into the reaction system
was then introduced ethylene to initiate polymerization. The
polymerization was effected at an ethylene pressure of 10
kg/cm.sup.2 and a temperature of 70.degree. C. for 30 minutes to
obtain 173 g of a polymer. The polymer exhibited an activity of
49.4 kg-polymer/g-complex.multidot.hr.multidot.atm.
The physical properties of the polymer thus obtained were as
follows:
Mw=705,000; Mw/Mn=4.16;
The polymer exhibited a density of 0.88 g/cm.sup.3. In DSC, no
peaks of enthalpy due to fusion and crystallization were
detected.
The measurement of .sup.13 C--NMR shows that the hexene content in
the polymer chain is 35.2% by weight and r.sub.1 r.sub.2 is
0.49.
EXAMPLE 12
Into a 1.5-l internal volume SUS autoclave the air in which had
been thoroughly replaced by nitrogen were introduced 3.2 ml of a
0.5 mol/l hexane solution of triisobutyl aluminum, 105 mg of the
silica-supported methylaluminoxane prepared in Example 3, a
solution of 0.69 mg of
dimethylsilylene(2-methyl-4-(1-naphthyl)indenyl)-(9-fluorenyl)
zirconium dichloride (IMNFZ) synthesized in Example 1 in 6 ml of
toluene, 90 g of 1-hexene, and 800 ml of isobutane. The reaction
mixture was then heated to a temperature of 70.degree. C. Into the
reaction system was then introduced a mixture (H.sub.2 /C.sub.2 (by
weight): 5.2.times.10.sup.-5) of ethylene and hydrogen to initiate
polymerization. The polymerization was effected at a mixture gas
pressure of 10 kg/cm.sup.2 and a temperature of 70.degree. C. for
30 minutes to obtain 191 g of a polymer. The polymer exhibited an
activity of 18.2 kg-polymer/g-complex.multidot.hr.multidot.atm.
The physical properties of the polymer thus obtained were as
follows:
HLMFR=1.85; Mw=251,000; Mw/Mn=4.20
The polymer exhibited a density of 0.88 g/cm.sup.3. In DSC, no
peaks of enthalpy due to fusion and crystallization were
detected.
The measurement of .sup.13 C--NMR shows that the hexene content in
the polymer chain is 35.7% by weight and r.sub.1 r.sub.2 is
0.51
EXAMPLE 13
Polymerization was effected in the same manner as in Example 12
except that the mixing gas ratio was altered. The polymerization
conditions and results are set forth in Table 3. The physical
properties of the polymer thus obtained are set forth in Table
4.
EXAMPLES 14 AND 15
Polymerization was effected in the same manner as in Example 12
except that the amount of 1-hexene to be used was altered. The
polymerization conditions and results are set forth in Table 3. The
physical properties of the polymer thus obtained are set forth in
Table 4.
EXAMPLES 16 AND 17
Polymerization was effected in the same manner as in Examples 11
and 15 except that IMPFZ was used as a metallocene compound. The
polymerization conditions and results are set forth in Table 3. The
physical properties of the polymer thus obtained are set forth in
Table 4.
COMPARATIVE EXAMPLE 9
Polymerization was effected in the same manner as in Example 11
except that isopropyridene(indenyl)(fluorenyl)-zirconium dichloride
(a) was used as a metallocene compound. The polymerization
conditions and results are set forth in Table 3. The physical
properties of the polymer thus obtained are set forth in Table
4.
COMPARATIVE EXAMPLES 10 AND 11
Polymerization was effected in the same manner as in Examples 11
and 12 except that bis(n-butylcyclopentadienyl)-zirconium
dichloride (b) was used as a metallocene compound. The
polymerization conditions and results are set forth in Table 3. The
physical properties of the polymer thus obtained are set forth in
Table 4.
COMPARATIVE EXAMPLES 12 AND 13
Polymerization was effected in the same manner as in Examples 11
and 12 except that ethylidenebis(indenyl)-zirconium dichloride (e)
was used as a metallocene compound. The polymerization conditions
and results are set forth in Table 3. The physical properties of
the polymer thus obtained are set forth in Table 4.
COMPARATIVE EXAMPLE 14
Polymerization was effected in the same manner as in Example 11
except that dimethylsilylenebis(tetrahydroindenyl)-zirconium
dichloride (f) was used as a metallocene compound. The
polymerization conditions and results are set forth in Table 3. The
physical properties of the polymer thus obtained are set forth in
Table 4.
The foregoing examples demonstrate that in the production of an
ethylenic copolymer the metallocene compound of the present
invention can provide a copolymer having a higher molecular weight
while maintaining the uniformity in the comonomer distribution. It
can also be seen that the catalyst system of the present invention
can provide a higher comonomer conversion (ratio of comonomer
incorporated in the polymer chain by the polymerization reaction to
comonomer charged) than the conventional metallocene catalyst
systems.
TABLE 3
__________________________________________________________________________
Ethylene Hydrogen Weight MAO/SiO.sub.2 TIBA pressure ratio 1-Hexene
Yield Activity Metallocene (mg) (mg) (ml) (Kg/cm.sup.2) (10.sup.-5
wt %) (g) (g) (Kg-PE/g-Zr .multidot. h .multidot. atm)
__________________________________________________________________________
Example 11 IMNFZ 0.69 36 1.1 10 0 90 173 49.4 Example 12 IMNFZ 2.06
105 3.2 10 5.2 90 191 18.2 Example 13 IMNFZ 3.10 160 4.9 10 17.3 90
189 12.2 Example 14 IMNFZ 3.13 160 4.9 10 17.3 24 120 7.7 Example
15 IMNFZ 3.13 160 4.9 10 17.3 15 95 6.1 Example 16 IMPFZ 2.66 148
4.5 10 0 90 215 15.9 Example 17 IMPFZ 3.21 180 5.5 10 17.3 10 113
7.1 Comparative a 2.44 167 5.1 10 0 90 58 4.8 Example 9 Comparative
b 1.18 95 2.9 10 0 90 108 18.8 Example 10 Comparative b 0.83 69 2.1
10 5.2 90 53 14.1 Example 11 Comparative e 2.52 197 6.0 10 0 90 37
3.0 Example 12 Comparative e 2.73 213 6.5 10 5.2 90 31 2.3 Example
13 Comparative f 3.12 223 6.8 10 0 90 23 1.5 Example 14
__________________________________________________________________________
TABLE 4
__________________________________________________________________________
Hexene MFR HLMFR Mw Density Tm Content (g/10 min) (g/10 min)
(.times.10.sup.-3) Mw/Mn (g/cm.sup.3) (.degree.C.) (%) r1r2
__________________________________________________________________________
Example 11 -- -- 705 4.16 <0.88 -- 35.2 0.44 Example 12 -- 1.85
251 4.20 <0.88 -- 35.7 0.51 Example 13 0.95 47.3 92 4.23
<0.88 -- 32.4 0.49 Example 14 1.52 38.2 99 4.53 0.907 104 10.3
0.45 Example 15 0.99 31.5 103 4.47 0.921 115 7.8 0.49 Example 16 --
-- 790 4.24 <0.88 -- 31.7 0.41 Example 17 0.70 18.7 115 4.21
0.915 110 8.7 0.39 Comparative 4.80 91 72 2.23 0.920 113 7.6 0.70
Example 9 Comparative 1.81 16 103 2.43 0.921 110 8.6 0.55 Example
10 Comparative 3.54 -- 72 2.73 0.925 111 8.3 0.61 Example 11
Comparative 1.03 122 113 3.57 0.905 103 12.5 0.73 Example 12
Comparative 3.32 -- 81 3.32 0.915 105 9.7 0.71 Example 13
Comparative 0.06 2.1 210 3.19 0.913 104 12.8 0.75 Example 14
__________________________________________________________________________
Preparation of Polypropylene Elastomer:
EXAMPLE 18
Into a 1.5-l internal volume SUS autoclave the air in which had
been thoroughly replaced by nitrogen was charged 11.7 ml of a 0.5 M
toluene solution of tri-i-butyl aluminum (TIBA). 8 mol of liquid
propylene was then charged into the autoclave. The reaction mixture
was then kept at a temperature of 30.degree. C. To a toluene
solution of 2.5 mg (0.039 mmol) of
dimethylsilylene(2-methyl-4-(1-naphtyl) indenyl) (9-fluorenyl)
zirconium dichloride (IMNFZ) synthesized in Example 1 was added 3.9
ml of a 0.5M toluene solution of TIBA. The reaction mixture was
then allowed to undergo reaction at a temperature of 30.degree. C.
for 5 minutes (Catalyst A). Further, 2.0 ml of a 2.9 mM toluene
solution of [Ph.sub.3 C][B(C.sub.6 F.sub.5).sub.4 ] (TPFPB) was
prepared (Catalyst B). Catalysts A and B were mixed, and then
immediately charged into the reaction vessel where polymerization
was then effected at a temperature of 50.degree. C. for 1 hour.
After the completion of the reaction, the resulting polypropylene
was dried in vacuo.
As a result, 240 g of a transparent amorphous polypropylene
elastomer was obtained. It exhibited an activity of 35
kg-PP/g-zr.multidot.h per metallocene.
The stereoregularity of the polymer thus obtained comprised mm=17%,
mr=47% and rr=36% (.sup.13 C--NMR spectrum in methyl region is set
forth in FIG. 2).
The polymer exhibited a molecular weight Mw of 593,000 and a
molecular weight distribution Mw/Mn of 2.8.
In DSC, no peaks of enthalpy due to fusion and crystallization were
detected.
EXAMPLE 19
The procedure of Example 18 was followed except that the
polymerization temperature was altered to 20.degree. C. and 1.1 mg
(0.0017 mmol) of dimethylsilylene(2-methyl-4-(1-naphtyl)-indenyl)
(9-fluorenyl)zirconium dichloride (IMNFZ) synthesized in Example 1
was used. As a result, 54 g of a transparent amorphous
polypropylene elastomer was obtained. The polymer thus obtained
exhibited an activity of 32 kg-PP/g-Zr.multidot.h per
metallocene.
mm=17%; mr=45%, rr=38%; Mw=853,000, Mw/Mn=2.8
EXAMPLE 20
The procedure of Example 18 was followed except that 1.2 mg (0.0020
mmol) of
dimethylsilylene(2-methyl-4-(1-phenylindenyl)(9-fluorenyl)zirconium
dichloride (IMPFZ) synthesized in Example 2 was used as a
metallocene compound. As a result, 125 g of a transparent amorphous
polypropylene elastomer was obtained. The polymer thus obtained
exhibited an activity of 61 kg-PP/g-Zr.multidot.h per
metallocene.
mm=16%; mr=46%, rr=38%; Mw=493,000, Mw/Mn=2.5
EXAMPLE 21
The procedure of Example 18 was followed except that the
polymerization temperature was altered to 20.degree. C. and 0.8 mg
(0.0014 mmol) of
dimethylsilylene(2-methyl-4-phenylindenyl)-(9-fluorenyl) zirconium
dichloride (IMPFZ) synthesized in Example 2 was used. As a result,
38 g of a transparent amorphous polypropylene elastomer was
obtained. The polymer thus obtained exhibited an activity of 28
kg-PP/g-Zr.multidot.h per metallocene.
mm=16%; mr=44%, rr=40%; Mw=793,000, Mw/Mn=2.5
None of the polymers obtained in Examples 17 to 19 showed peaks of
enthalpy due to fusion and crystallization.
COMPARATIVE EXAMPLE 15
The procedure of Example 18 was followed except that 0.77 mg
(0.0016 mmol) of isopropyridene(1-indenyl)-(9-fluorenyl) zirconium
dichloride (a) was used.
As a result, 17 g of an oily atactic polypropylene was obtained.
The polymer thus obtained exhibited activity of 22
kg-PP/g-Zr.multidot.h per metallocene compound.
mm=27%; mr=33%; rr=40%; Mw=5,200; Mw/Mn=2.8
COMPARATIVE EXAMPLE 16
The procedure of Example 18 was followed except that 0.92 mg
(0.0017 mmol) of isopropyridene(3-t-butyl-1-indenyl)-(9-fluorenyl)
zirconium dichloride (g) was used.
As a result, 19 g of a powdered isotactic polypropylene was
obtained. The polymer thus obtained exhibited activity of 21
kg-PP/g-Zr.multidot.h per metallocene compound.
mm=78%; mr=12%; rr=10%; Mw=214,000; Mw/Mn=2.6
The foregoing examples demonstrate that among the crosslinked
metallocene compound groups having indene ring and fluorene ring,
the group having substituents of the present invention can form a
catalyst which specifically enables the production of a
polypropylene elastomer.
EXAMPLE 22
1.8 g (2.8 mmol) of
dimethylsilylene(2-methyl-4-(1-naphthyl)indenyl)
(9-fluorenyl)zirconium dichloride (IMNFZ) and 10 mg (0.014 mmol) of
rac-dimethylsilylene-(2-methyl-4-(1-naphthyl)indenyl) zirconium
dichloride (h) were dissolved in 100 ml of toluene (distilled and
dried in the presence of Na-K alloy). 0.10 ml of the toluene
solution thus obtained was then subjected to propylene
polymerization at a temperature of 60.degree. C. in the same manner
as in Example 18. As a result, 72 g of a transparent polypropylene
elastomer was obtained. The polymer thus obtained exhibited an
activity of 40 kg-PP/g-Zr.multidot.h per metallocene compound.
mm=25%; mr=42%; rr=33% (.sup.13 C--NMR spectrum in methyl region is
set forth in FIG. 3)
Mw=428,000; Mw/Mn=5.2
In DSC, the polymer showed a melting point at 146.4.degree. C.
EXAMPLE 23
The procedure of Example 22 was followed except that 0.13 ml
(0.0035 mmol per mol of metallocene compound used) of a toluene
solution of metallocene compound was used and the polymerization
temperature was altered to 70.degree. C. As a result, 78 g of a
transparent polypropylene elastomer was obtained. The polymer thus
obtained exhibited an activity of 35 kg-PP/g-Zr.multidot.h per
metallocene compound.
mm=28%; mr=41%; rr=31%; Mw=320,000; Mw/Mn=8.9
In DSC, the polymer showed a melting point at 146.2.degree. C.
The results are set forth in Tables 5 and 6.
The polypropylene products obtained in Examples 18 to 23 were then
subjected to elasticity test. The results are set forth in Table 7.
The stress-strain curve of polypropylenes obtained in Examples 18
and 22 are set forth in FIGS. 4 and 5, respectively.
TABLE 5
__________________________________________________________________________
Polymerization Weight TPFPB TIBA temperature Yield Activity
Metallocene 1 Metallocene 2 (.mu.mol) (ml) (ml) (.degree.C.) (g)
(Kg-PP/g-Zr .multidot. h) Remarks
__________________________________________________________________________
Example 18 IMNFZ -- 3.9 2.0 15.6 50 240 96 elastic Example 19 IMNFZ
-- 1.7 0.9 6.8 20 54 32 elastic Example 20 IMPFZ -- 2.0 1.0 8.0 50
125 61 elastic Example 21 IMPFZ -- 1.4 0.7 5.6 20 38 28 elastic
Comparative a 1.6 0.8 6.4 20 20 17 22 oily Example 15 Comparative g
-- 1.7 0.9 6.8 20 19 21 powder Example 16 Example 22 IHNFZ h 2.8
1.4 11.2 60 72 40 elastic Example 23 IMNFZ h 3.5 1.8 14.0 70 78 35
elastic
__________________________________________________________________________
TABLE 6 ______________________________________ mm mr rr Mw Tm
.DELTA.H (%) (%) (%) (.times.10.sup.-3) Mw/Mn (.degree.C.) (J
.multidot. g.sup.-1) ______________________________________ Example
18 17 47 36 593 2.8 -- -- Example 19 17 45 38 853 2.8 -- -- Example
20 16 46 38 493 2.5 -- -- Example 21 16 44 40 793 2.5 -- --
Comparative 27 33 40 5.0 2.8 -- -- Example 15 Comparative 78 12 10
214 2.6 100 24.7 Example 16 Example 22 25 42 33 428 5.2 146 11.1
Example 23 28 41 31 320 8.9 146 13.4
______________________________________
TABLE 7
__________________________________________________________________________
Stress Tensile Tensile at 100% Elongation at stress at Elongation
stress at Elongation Internal elongation yield point yield point at
rupture rupture set haze (MPa) (%) (MPa) (%) (MPa) (%) (%)
__________________________________________________________________________
Example 18 1.0 136 1.0 >2,000 <0.33 45 10.5 Example 19 1.1
145 1.2 >2,000 <0.35 40 10.1 Example 20 0.9 131 0.9 >2,000
<0.32 47 10.2 Example 21 1.2 143 1.3 >2,000 <0.35 39 10.4
Example 22 1.8 -- -- 1,870 4.46 16 13.1 Example 23 1.7 -- -- 1,910
3.38 13 14.5
__________________________________________________________________________
As mentioned above, the polymerization of an olefin in the presence
of a metallocene compound as an essential catalyst component
provides a plurality of effects depending on the olefin to be
polymerized.
In other words, in the case of the production of an ethylenic
polymer, a high melt tension polymer having up to a high molecular
weight can be produced.
In the case of the production of an ethylenic copolymer, a polymer
having a uniform comonomer distribution can be produced up to a
high molecular weight range. Further, a high percent comonomer
incorporation in the polymer chain can be provided, giving an
advantage in cost.
In the case of the polymerization of .alpha.-olefin, particularly
propylene, an amorphous polypropylene having elastic properties can
be produced at a high activity. When the polymerization is effected
in the presence of the metallocene compound of the present
invention combined with other metallocene compounds, the elastic
properties of the polymer thus produced can be properly controlled
under industrially effective polymerization conditions.
While the invention has been described in detail and with reference
to specific examples thereof, it will be apparent to one skilled in
the art that various changes and modifications can be made therein
without departing from the spirit and scope thereof.
* * * * *